TWI419992B - Delivery device for thin film deposition - Google Patents

Description

Conveying device for film deposition

The present invention is generally directed to deposition of thin film materials and, more particularly, to apparatus for atomic layer deposition on a substrate using a dispensing head that simultaneously directs gas flow to the substrate.

One of the techniques widely used for thin film deposition is chemical vapor deposition (CVD) using chemically reactive molecules that react in a reaction chamber to deposit a desired film on a substrate. Molecular precursors suitable for CVD applications comprise the elemental (atomic) component of the film to be deposited and typically also include other elements. The CVD precursor is a volatile molecule that is delivered to the chamber in the form of a gas phase to react at the substrate to form a thin film thereon. The chemical reaction allows the deposition of a film having the desired film thickness.

Most CVD techniques typically require the application of a well-controlled flow of one or more molecular precursors to the CVD reactor. The substrate is maintained at a well controlled temperature and under controlled pressure conditions to promote chemical reactions between the molecular precursors while effectively removing by-products. Obtaining optimal CVD performance requires the ability to achieve steady state airflow, temperature and pressure conditions throughout the process and the ability to minimize or eliminate transients.

Especially in the field of semiconductors, integrated circuits and other electronic devices, there are higher quality, denser films for films, in particular having superior conformal coating properties beyond the achievable limits of conventional CVD techniques, especially at low temperatures. The demand for the film produced.

Atomic Layer Deposition ("ALD") is available for comparison with its CVD precursor method Alternative thin film deposition techniques with improved thickness resolution and conformality. The ALD method divides a conventional thin film deposition process of conventional CVD into a single atomic layer deposition step. Advantageously, the ALD step is self-terminating and an atomic layer can be deposited when performed until or beyond the self-terminating exposure time. The atomic layer is typically in the range of 0.1 to 0.5 molecular monolayers, with typical dimensions not exceeding several angstroms (Angstrom). In ALD, the deposition of an atomic layer is the result of a chemical reaction between the reactive molecular precursor and the substrate. In each individual ALD reaction-deposition step, the net reaction allows the desired atomic layer to be deposited and substantially eliminates the "extra" atoms originally included in the molecular precursor. In its purest form, ALD involves the adsorption and reaction of each precursor in the absence of other precursors of the reaction. In practice, it is difficult to avoid some direct reaction of different precursors that cause a small amount of chemical vapor deposition reaction in any system. The goal of any system that claims to perform ALD is to achieve device performance and characteristics commensurate with the ALD system while recognizing that a small number of CVD reactions can be tolerated.

In ALD applications, two molecular precursors are typically introduced into the ALD reactor in separate stages. For example, the metal precursor molecule ML _x contains a metal element M bonded to an atom or a molecular ligand L. For example, M can be, but is not limited to, Al, W, Ta, Si, Zn, and the like. When the surface of the substrate is prepared to directly react with the molecular precursor, the metal precursor reacts with the substrate. For example, the surface of the substrate is typically prepared to include a hydrogen-containing ligand AH or an analog thereof that is reactive with a metal precursor. Sulfur (S), oxygen (O) and nitrogen (N) are some typical A substances. The gaseous metal precursor molecule effectively reacts with all of the ligands on the surface of the substrate, resulting in the deposition of a single atomic layer of the metal: substrate - AH + ML _x → substrate - AML _x-1 + HL (1) where HL is the reaction pair product. During the reaction, the initial surface ligands consumed AH and the surface becomes covered with L ligands, which can not further react with metal precursor ML _x. Thus, when all of the initial AH ligands on the surface are replaced by AML _x-1 species, the reaction terminates spontaneously. The reaction stage is typically followed by an inert gas purification stage that eliminates excess metal precursor from the chamber, followed by independent introduction of a second reactive gaseous precursor material.

A second molecular precursor is then used to restore the surface reactivity of the substrate to the metal precursor. This is done, for example, by removing the L ligand and redepositing the AH ligand. Under such conditions, the second precursor typically contains the desired (usually non-metallic) elements A (i.e., O, N, S) and hydrogen (i.e., H ₂ O, NH ₃ , H ₂ S). The subsequent reaction is as follows: Substrate-A-ML+AH _Y → Substrate-AM-AH+HL (2) This converts the surface back to its state covered with AH. (The chemical reaction is not balanced here for simplicity.) The other elements A required are incorporated into the film and the improper ligand L is eliminated as a volatile by-product. Again, the reaction consumes the reactive site (this time is the site capped with L) and self-terminates when the reactive sites on the substrate are completely depleted. The second molecular precursor is then removed from the deposition chamber by flowing the inert purge gas in the second purge stage.

Therefore, in summary, the basic ALD method requires the chemicals to alternately flow to the substrate in sequence. A representative ALD method as discussed above is a cycle with four different stages of operation: 1. ML _x reaction; 2. ML _x purification; 3. AH _y reaction; and 4. AH _y purification, and then back to stage 1 .

This alternates the surface removal reaction with the removal of the substrate surface to its original reaction state and the repetitive order of the purification operation is a typical ALD deposition cycle. A key feature of ALD operation is the restoration of the substrate to its initial surface chemistry. Using this repeating set of steps, the film can be laminated to the substrate in equal metering layers that are similar in terms of chemical kinetics, deposition per cycle, composition and thickness.

ALD can be used as a fabrication step for forming a variety of thin film electronic devices including semiconductor devices and supporting electronic components such as resistors and capacitors, insulators, bus bars, and other conductive structures. ALD is particularly suitable for forming thin layers of metal oxides in components of electronic devices. Typical types of functional materials that can be used for ALD deposition include conductors, dielectrics or insulators, and semiconductors.

The conductor can be any suitable electrically conductive material. For example, the conductor may comprise a transparent material such as indium tin oxide (ITO), doped zinc oxide ZnO, SnO ₂ or In ₂ O ₃ . The thickness of the conductor can vary, and it can range from 50 to 1000 nm, depending on the particular example.

Examples of suitable semiconducting materials are compound semiconductors such as gallium arsenide, gallium nitride, cadmium sulfide, intrinsic zinc oxide and zinc sulfide.

The dielectric material electrically insulates portions of the patterned circuit. The dielectric layer can also be referred to as an insulator or an insulating layer. Specific examples of materials suitable for use as dielectrics include citrate, citrate, titanate, zirconate, alumina, cerium oxide, cerium oxide, cerium oxide, titanium oxide, zinc selenide, and zinc sulfide. . In addition, Alloys, combinations and multilayers of these examples can also be used as dielectrics. Alumina is preferred in these materials.

The dielectric structure layer may comprise two or more layers having different dielectric constants. Such insulators are discussed in U.S. Patent No. 5,981,970 and U.S. Patent Application Serial No. 11/088,645. Dielectric materials typically exhibit an energy band gap greater than 5 eV. The thickness of the suitable dielectric layer can vary, and can range from 10 to 300 nm, depending on the particular example.

A variety of device structures having functional layers as described above can be prepared. The resistor can be fabricated by selecting a conductive material having a medium to poor electrical conductivity. Capacitors can be fabricated by placing a dielectric between two conductors. The diode can be prepared by placing two complementary carrier type semiconductors between the two conductive electrodes. An intrinsic semiconductor region can also be placed between the complementary carrier type semiconductors, indicating that the region has a smaller number of free charge carriers. The diode can also be constructed by placing a single semiconductor between two conductors, where one of the conductor/semiconductor interfaces produces a Schottky barrier that strongly blocks current in one direction. The transistor can be prepared by placing an insulating layer on a conductor (gate) and then placing a semiconductive layer. A transistor can be formed if two or more additional conductor electrodes (source and drain) are placed in contact with the top semiconductor layer at intervals. Any of the above devices can be formed in a variety of configurations as long as the necessary interface is formed.

In typical applications for thin film transistors, switches are needed that control the flow of current through the device. Therefore, it is necessary to flow a high current through the device when the switch is turned on. The degree of current is related to the semiconductor charge carrier mobility. When closed When the device is used, it is desirable that the current is extremely small. This is related to the charge carrier concentration. In addition, visible light generally has little or no effect on the response of the thin film transistor. To achieve this, the semiconductor bandgap should be sufficiently large (>3 eV) so that exposure to visible light does not result in band-to-band transitions. The material capable of generating high mobility, low carrier concentration, and high energy band gap is ZnO. In addition, for mass production on moving webs, it is highly desirable that the chemicals used in the process be inexpensive and have low toxicity, which can be met by using ZnO and most of its precursors.

Self-saturating surface reactions make ALD relatively unimportant to transmission non-uniformity, otherwise due to engineering tolerances and limitations of the flow system or related to surface configuration (ie, deposition in three-dimensional, high aspect ratio structures), Will damage surface uniformity. In general, the non-uniform flux of chemicals in the reaction process typically results in different completion times on different portions of the surface region. However, ALD allows each reaction to be completed over the entire substrate surface. Therefore, the difference in completion kinetics does not result in a loss of uniformity. This is because the region where the reaction is first completed terminates the reaction by itself; other regions can continue until the entire treated surface undergoes the desired reaction.

Typically, the ALD process deposits a 0.1-0.2 nm film in a single ALD cycle (one cycle has the steps numbered 1 to 4 as previously listed). Appropriate and economically viable cycle times should be achieved to provide uniform film thicknesses in the range of 3 nm to 30 nm for many or most semiconductor applications, and to provide even thicker films for other applications. The substrate is preferably processed within 2 minutes to 3 minutes according to industrial productivity standards, which means that the ALD cycle time should be in the range of 0.6 seconds to 6 seconds.

ALD presents considerable promise for providing a controlled degree of highly uniform film deposition. However, despite its inherent technical capabilities and advantages, there are still several technical hurdles. An important consideration is the number of cycles required. Due to its repeated reactants and purification cycles, the effective use of ALD requires equipment that can suddenly change the chemical flowing from ML _x to AH _y and quickly perform a purification cycle. Conventional ALD systems are designed to circulate different gaseous materials to a substrate in the desired order. However, it is difficult to obtain a reliable solution for introducing a series of desired gaseous formulations into the chamber at the desired speed and without some improper mixing. In addition, ALD equipment should be able to perform this fast procedure efficiently and reliably over many cycles to enable cost effective coating of many substrates.

In an effort to minimize the time required for the ALD reaction to self-terminate at any given reaction temperature, one method uses a so-called "pulse" system to maximize the flux of chemicals flowing into the ALD reactor. In order to maximize the flux of chemicals entering the ALD reactor, it is advantageous to introduce the molecular precursor into the ALD reactor with minimal dilution of the inert gas and under high pressure. However, such measures have a negative impact on achieving short cycle times and the requirement to rapidly remove such molecular precursors from the ALD reactor.

The rapid removal in turn requires that the gas residence time in the ALD reactor be minimized. The gas residence time τ is proportional to the reactor volume V, the pressure P in the ALD reactor, and the reciprocal of the flow rate Q, ie: τ = VP / Q (3)

In a typical ALD chamber, volume (V) and pressure (P) are independently determined by mechanical and pumping limiting factors, making it difficult to accurately control residence time. Low value. Thus, reducing the pressure (P) in the ALD reactor contributes to shorter gas residence times and increases the rate of removal (purification) of the chemical precursor from the ALD reactor. In contrast, reducing the ALD reaction time to a minimum requires maximizing the flux of the chemical precursor entering the ALD reactor by using high pressure in the ALD reactor. In addition, gas residence time and chemical use efficiency are inversely proportional to the flow rate. Therefore, although reducing the flow rate can increase the efficiency, it also increases the gas residence time.

Existing ALD methods have been compromised by the compromise between the need to reduce reaction time and improve chemical utilization efficiency and the need to minimize purge gas retention and chemical removal time on the other hand. One method of overcoming the inherent limitations of "pulsed" delivery of gaseous materials is to continuously provide each reactive gas and move the substrate through each gas in succession. For example, U.S. Patent No. 6,821,563 to the name of U.S. Patent No. 6,821,563, issued to U.S. Pat. The vacuum pump orifices operate alternately. Each air vent directs its airflow vertically downward toward the substrate. The independent air flow is separated by a wall or a partition, and a vacuum pump for exhausting air is located on both sides of each air flow. The lower portion of each of the spacers extends close to the substrate, for example 0.5 mm or more from the surface of the substrate. In this manner, the lower portion of the separator is separated from the surface of the substrate by a distance sufficient to cause the gas flow to flow around the lower portion toward the vacuum orifice after the gas stream reacts with the surface of the substrate.

A rotary turntable or other transport device is provided to hold one or more substrate wafers. Use this configuration to make the substrate under different airflows The square reciprocates to achieve ALD deposition there. In an embodiment, the substrate is moved through the chamber in a linear path wherein the substrate is passed back and forth several times.

Another method of using a continuous gas stream is shown in U.S. Patent No. 4,413,022, issued to the name of s. The airflow array has alternating source gas openings, carrier gas openings, and vacuum exhaust openings. The reciprocating motion of the substrate on the array again enables ALD deposition without the need for pulsed operation. In particular, in the embodiment of Figures 13 and 14, the continuous interaction between the substrate surface and the reactive vapor is achieved by the reciprocating motion of the substrate on a fixed array of source openings. The diffusion barrier is formed by having a carrier gas opening between the exhaust openings. Although little or no detail is provided in the method or example, Suntola et al. state that the operation of using this embodiment may be achieved even at atmospheric pressure.

While systems such as those described in the '563 Yudovsky and '022 Suntola et al. disclosures avoid certain difficulties inherent in pulsed gas processes, such systems have other disadvantages. The airflow delivery unit of the '563 Yudovsky Revelation or the airflow array disclosed by the '022 Suntola et al. may not be used at a distance of less than 0.5 mm from the substrate. The airflow delivery devices disclosed in the '563 Yudovsky and '022 Suntola et al. patents are not configured to be possible for moving the web surface, such as may be used as a flexible substrate for forming, for example, electronic circuits, photoreceptors or displays. . The complex configuration of the airflow delivery unit of the '563 Yudovsky Revelation, which provides both airflow and vacuum, and the airflow array of the '022 Suntola et al. disclosure make these solutions difficult to implement and Mass production is costly and limits its potential availability for deposition applications on mobile substrates of limited size. In addition, it is extremely difficult to maintain a uniform vacuum at different points in the array and to maintain a synchronized gas flow and vacuum at a complementary pressure, thereby compromising the uniformity of the gas flux provided to the surface of the substrate.

An atmospheric pressure atomic layer chemical vapor deposition method is disclosed in U.S. Patent Publication No. 2005/0084610 to Selitser. Selitser et al. state that an abnormal increase in reaction rate is obtained by changing the working pressure to atmospheric pressure, which will involve several orders of magnitude increase in reactant concentration, and thus enhance the surface reaction rate. Although Figure 10 of 2005/0084610 shows an embodiment in which the chamber walls are removed, the embodiment of Selitser et al. relates to a separate chamber for each stage of the method. A series of separate syringes are spaced around the rotating circular substrate holder track. Each syringe has an independently operated reactant, purge and exhaust manifold and controls and acts as a complete monolayer deposition and reactant purge cycle for each substrate transported beneath it during the process. Although Selitser et al. state that the spacing of the syringes is selected such that by purging the gas stream to prevent cross-contamination from adjacent injectors and incorporating the exhaust manifold in each syringe, they describe very few specific details of the gas injector or manifold or Describe specific details of a gas injector or manifold.

A typical diffuser system for gases will diffuse the gas isotropically. In view of the design of the coating head, it is advantageous in that it can provide flow uniformity. However, in an ALD system such as the '563 Yudovsky, this diffusion will allow the gas to diffuse laterally, which will adversely result in a reaction between adjacent gas streams.

An ALD processing device such as described above and the aforementioned US 11/392,006 Both the lateral flow ALD device and the above-described U.S. Patent No. 11/620,738 floating head ALD device provide spatial isolation of mutually reactive gases. The efficiency of such devices is further improved by placing such gases relatively closely adjacent but still not mixing due to, for example, the presence of a purge stream and the use of one or more of a particular flow pattern. When attempting to bring these gases in close proximity, it is critical to deliver the gas in a relatively uniform manner with good uniformity over the size of the delivery head.

It is an object of the present invention to deliver a gas with good uniformity in the size of the delivery head in a relatively precise manner when the reactive gas is placed in close proximity in the ALD coating process.

Another object of the invention is to diffuse the gases as they are maintained during the simultaneous flow of the gas.

Another object is to provide a uniform back pressure across the extended area of the output channel in providing this uniformity, thereby diffusing the gas flow.

Another object is to provide an efficient and easy to assemble diffuser system for the delivery head.

Another object is to provide an ALD deposition method and apparatus that can be used in a continuous process and that provides improved gas flow separation over previous solutions.

Another object is to provide an ALD deposition method and apparatus that is more robust to potential disturbances or inhomogeneities in process conditions or environments during operation.

Another object is to provide an ALD deposition method and apparatus that advantageously provides improved mobility in embodiments using a floating delivery head.

The invention provides an apparatus and method for depositing a film material on a substrate, The method comprises simultaneously directing a series of gas streams from an output face of the delivery head of the thin film deposition system toward the surface of the substrate, wherein the series of gas streams comprises at least a first reactive gaseous material, an inert purge gas, and a second reactive gaseous material. The first reactive gaseous material is capable of reacting with the surface of the substrate treated with the second reactive gaseous material. In particular, the present invention relates to a transport apparatus for depositing a thin film material on a substrate, comprising: a transport apparatus for depositing a thin film material on a substrate, comprising: (a) a plurality of air inlets, respectively Receiving at least a first air inlet, a second air inlet, and a third air inlet of a common supply of the first gaseous material, the second gaseous material, and the third gaseous material; (b) at least one capable of receiving deposition from the thin film material An exhaust port of the exhaust gas and at least two extended exhaust passages, each of the extended exhaust passages being in gaseous communication with the at least one exhaust port; (c) at least three sets of extended injection passages, (i) the first group comprising One or more first extended injection channels, (ii) the second set includes one or more second extended injection channels, and (iii) the third set includes at least two third extended injection channels, first and second Each of the third extended injection passages is in gaseous fluid communication with one of the respective first, second, and third intake ports; wherein the first, second, and third extensions Each of the jet channels and extension Each of the gas passages extends substantially parallel in the length direction; wherein each of the first extended spray passages has a relatively proximally extending exhaust passage and a relatively farther third extended injection passage on the at least one extended side thereof Separating the second extended jet channels; Wherein each of the first extended jet channels and each of the second extended jet channels are located between the relatively closer extended exhaust channels and between the relatively far extended jet channels; and (d) a gas diffuser with three sets of extended jets At least one of the channels is associated such that at least one of the first, second, and third gaseous materials are respectively capable of passing through the gas diffuser prior to delivery of the thin film material on the substrate from the transport device to the substrate, and wherein The gas diffuser maintains flow separation downstream of each of the at least one set of extended injection passages by at least one of the first, second, and third gaseous materials.

Thus, the delivery device can comprise a single first extended injection channel, a single second extended injection channel, and two or more third extended injection channels, but as described below, a plurality (two or more) of each extended injection channel It is better. Thus the term "group" can include a single member.

The delivery head preferably includes a plurality of first extended injection channels and/or a plurality of second extended injection channels for various applications. However, the single stage delivery head can have, for example, at least one metal and/or one oxidant channel and at least two purification channels. A plurality of individual "head subunits" that are connected together or that are simultaneously transported during film deposition on a substrate or that process the same substrate for a common period of time, even if constructed separately or may be separated after deposition, for purposes of the present invention It is considered a "delivery head".

In a preferred embodiment, the first and second gaseous materials may be mutually reactive gases, and the third gaseous material may be a purge gas such as nitrogen.

In a particularly advantageous aspect of the invention, it is assumed that the representative gas is nitrogen at 25 ° C and the representative average velocity of the gaseous material passing through the gas diffuser is between 0.01 and 0.5 m/sec, the gas diffuser can provide A friction coefficient greater than 1 × 10 ² .

In an embodiment of the invention, the gas diffuser comprises a porous material through which at least one of the first, second, and third gaseous materials passes.

In a second embodiment of the invention, a gas diffuser comprises a mechanically formed assembly comprising at least two elements, each element comprising substantially parallel surface regions opposite each other, each element comprising a respective and at least one set of extensions One of the injection passages individually extends the interconnecting passage of the injection passage in fluid communication, wherein the gas diffuser is provided by providing two substantially vertical flow paths for the gaseous material separated by a substantially horizontal flow path for the gaseous material A deflection of the gaseous material therethrough, wherein the substantially vertical flow path is provided by one or more passages extending in the direction of extension and wherein the substantially horizontal flow path is narrowed between parallel surface regions of the two elements Space is provided, where vertical refers to the orthogonal direction relative to the output face of the delivery device.

In a preferred embodiment, the gas diffuser is associated with each of the three sets of extended jet channels such that each of the first, second and third gaseous materials is capable of independently forming a film on the substrate The material is transferred from the delivery device to the substrate during deposition, and wherein the gas diffuser maintains flow separation downstream of each of the three sets of extended injection channels for each of the first, second, and third gaseous materials.

Another aspect of the invention is directed to a deposition system wherein the delivery device is capable of providing a thin film deposition of solid material on a substrate in a system, wherein the deposition surface of the delivery head is maintained between the output surface of the delivery head and the substrate surface during film deposition Generally uniform distance.

Another aspect of the invention relates to a method of depositing a thin film material on a substrate, comprising simultaneously directing a series of gas streams from an output face of the transfer head toward a surface of the substrate, and wherein the series of gas streams comprises at least a first reactivity A gaseous material, an inert purge gas, and a second reactive gaseous material, and wherein the first reactive gaseous material is capable of reacting with a surface of the substrate treated with the second reactive gaseous material. The delivery head includes a gas diffuser element through which at least one (preferably all three) of the first reactive gaseous material, the inert purge gas, and the second reactive gaseous material are delivered while maintaining the flow of the at least one gaseous material Separation. Advantageously, the gas diffuser provides a coefficient of friction greater than 1 x 10 ² for the gaseous material passing therethrough, thereby providing a counter pressure and recirculating the flow of at least one of the first, second and third gaseous materials from the delivery device Promote pressure balance.

The coefficient of friction assumes that the area of the characteristic friction coefficient is equal to the total area between the discharge extension channels on either side of each of the at least one set of injection extension channels, thereby providing a back pressure and at least one of the first and second And the flow of the third gaseous material exits the delivery device to promote pressure balance.

In a preferred embodiment, one or more of the gas streams provide a pressure that at least causes the surface of the substrate to separate from the end faces of the delivery head.

In another embodiment, the system provides relative oscillatory motion between the dispensing head and the substrate. In a preferred embodiment, the system can be operated with continuous movement of the substrate subjected to film deposition, wherein the system can preferably carry the carrier on the web at substantially atmospheric pressure in a surrounding unsealed environment or The carrier in the form of a web is conveyed through the dispensing head.

An advantage of the present invention is that it provides a compact device for atomic layer deposition on a substrate that is well suited for several different types of substrates and deposition environments.

Another advantage of the present invention is that it allows operation under atmospheric conditions in the preferred embodiment.

Another advantage of the present invention is that it is suitable for deposition on webs or other moving substrates, including deposition on large area substrates.

Another advantage of the present invention is that it can be used in low temperature processes at atmospheric pressure, which can be carried out in an unsealed environment that is open to the surrounding atmosphere. The method of the present invention allows the gas residence time τ to be controlled in the relationship previously shown in equation (3), thereby allowing the residence time τ to be shortened if the system pressure and volume are controlled by a single variable gas flow.

The terms "vertical", "horizontal", "top", "bottom", "front", "back" or "parallel" and the like, as used herein, refer to a conveyor in a theoretical configuration, unless otherwise stated. The front/bottom horizontal end face or the top horizontal parallel surface of the treated substrate, in which the delivery head is vertically above the substrate, but the theoretical configuration is optional, for example the substrate can be positioned over the end of the delivery head or Other ways to locate.

These and other objects, features and advantages of the present invention will become apparent from the <RTIgt;

The present description relates in particular to elements which form part of the device according to the invention or cooperate directly with the device according to the invention. It will be appreciated that elements not specifically shown or described may be familiar to those skilled in the art. Forms.

For the purposes of the following description, the term "gas" or "gaseous material" is used broadly to encompass any of a variety of gasified or gaseous elements, compounds or materials. Other terms as used herein (such as "reactant", "precursor", "vacuum" and "inert gas") have their well-understood meaning as fully understood by those skilled in the art of material deposition. The drawings are not to scale, but are intended to illustrate the overall function and structural configuration of certain embodiments of the invention. The terms "upstream" and "downstream" have their conventional meanings related to the direction of the gas flow.

The apparatus of the present invention exhibits a significant deviation of conventional methods from ALD by using a modified dispensing device that delivers a gaseous material to the surface of the substrate, the device being adapted for larger, web-based or web-supported substrates Upper deposition and ability to achieve highly uniform film deposition at improved production rates. The apparatus and method of the present invention uses continuous (as opposed to pulsed) gaseous material distribution. The apparatus of the present invention allows operation at or near atmospheric pressure as well as under vacuum and can operate in an unsealed or open environment.

Referring to Figure 1, a cross-sectional side view of one embodiment of a delivery head 10 for atomic layer deposition on a substrate 20 in accordance with the present invention is shown. The delivery head 10 has an intake conduit 14 that serves as an intake port for receiving a first gaseous material, an intake conduit 16 for receiving an intake port of a second gaseous material, and an intake port for receiving a third gaseous material. Air duct 18. These gases are ejected at the output face 36 via an output channel 12 having a structural configuration as described later. The dotted arrows in FIG. 1 and subsequent FIGS. 2-3B refer to the delivery of gas from the delivery head 10 to the substrate 20. In Figure 1, arrow X also indicates the exhaust path (shown upwardly in this figure) and the exhaust passage in communication with the exhaust conduit 24 that provides the exhaust port. twenty two. For simplicity of description, the exhaust is not shown in Figures 2-3B. Since the effluent gas can still contain a large amount of unreacted precursor, it may be improper to allow the vent gas stream containing primarily one reactive species to mix with the gas stream containing primarily the other material. Thus, it will be appreciated that the delivery head 10 can include a number of separate vents.

In one embodiment, the intake conduits 14 and 16 are adapted to receive first and second gases that are sequentially reacted on the surface of the substrate to effect ALD deposition, and the intake conduit 18 is inert to the first and second gases Purify the gas. The delivery head 10 is spaced from the substrate 20 by a distance D which can be provided on the substrate carrier as described in more detail below. Reciprocating motion can be provided between the substrate 20 and the delivery head 10 by moving the substrate 20, by moving the delivery head 10, or by moving the substrate 20 and the delivery head 10. In the particular embodiment illustrated in FIG. 1, substrate 20 is moved in a reciprocating manner across output face 36 by substrate carrier 96, as indicated by arrow A in FIG. 1 and the phantom outline on the right and left sides of substrate 20. It should be noted that reciprocating motion is not always necessary for film deposition using the delivery head 10. Other types of relative motion between the substrate 20 and the delivery head 10 can also be provided, such as movement of the substrate or delivery head 10 in one or more directions, as described in more detail below.

The cross-sectional view of Figure 2 shows the gas stream ejected on a portion of the output face 36 of the delivery head 10 (with the exhaust path omitted as previously described). In this particular configuration, each output channel 12 is in gaseous fluid communication with one of the intake conduits 14, 16 or 18 as seen in FIG. Each output channel 12 typically delivers a first reactive gaseous material O or a second reactive gaseous material M or a third inert gaseous material I.

Figure 2 shows a relatively basic or simple gas configuration. It is envisioned that a plurality of streams of a non-metallic deposition precursor (e.g., material O) or a plurality of streams of a metal-containing precursor material (e.g., material M) may be sequentially delivered at each orifice in a single deposition of the film. Alternatively, when forming a composite film material, such as having alternating metal layers or mixing a smaller amount of dopants in the metal oxide material, a mixture of reactive gases (eg, a mixture of metal precursor materials or metals and non-metals) A mixture of metal precursors) is applied to a single output channel. Importantly, an intermediate stream, labeled as an inert gas, also referred to as a purge gas, is separated by any reactant channels in which the gases may react with each other. The first and second reactive gaseous materials O and M react with each other to effect ALD deposition, but none of the reactive gaseous materials O or M react with the inert gaseous material I. The nomenclature used in Figure 2 and subsequent figures indicates some typical types of reactive gases. For example, the first reactive gaseous material O can be an oxidizing gaseous material; the second reactive gaseous material M will be a metal containing compound, such as a zinc containing material. The inert gaseous material I can be nitrogen, argon, helium or other gases commonly used as purge gases in ALD systems. The inert gaseous material I is inert to the first or second reactive gaseous materials O and M. The reaction between the first and second reactive gaseous materials will form a metal oxide or other binary compound for use in a semiconductor, such as zinc oxide ZnO or ZnS, in one embodiment. The reaction between two or more reactive gaseous materials can form a ternary compound, such as ZnAlO.

3A and 3B are cross-sectional views showing the ALD coating operation performed when the substrate 20 is passed through the output face 36 of the delivery head 10 for transporting the reactive gaseous materials O and M. In FIG. 3A, the surface of the substrate 20 first receives continuous ejection of the output channel 12 that is assigned to deliver the first reactive gaseous material O. Oxidized material. The surface of the substrate now contains a partially reactive form of material O which readily reacts with material M. Subsequently, when the substrate 20 enters the path of the metal compound of the second reactive gaseous material M, it reacts with M to form a metal oxide or some other thin film material that can be formed from the two reactive gaseous materials. Unlike conventional solutions, the deposition order shown in Figures 3A and 3B is continuous, rather than pulsed, for a given substrate or its particular region during deposition. That is, when the substrate 20 traverses the surface of the delivery head 10 or conversely when the delivery head 10 passes along the surface of the substrate 20, the materials O and M are continuously ejected.

As shown in Figures 3A and 3B, in the alternate output channel 12, an inert gaseous material I is provided between the first and second reactive gaseous materials O and M. It is noted that, as shown in FIG. 1, there are exhaust passages 22, but preferably there are no vacuum passages interspersed between the output passages 12. It is only necessary to provide a small amount of extraction force of the exhaust passage 22 to discharge the exhaust gas that is injected from the delivery head 10 and used for processing.

In one embodiment, as described in more detail in the co-pending U.S. Patent No. 11/620,744, the substrate 20 is provided with gas pressure such that at least in part by the force of the applied pressure. Keep the spacing D. By maintaining a certain amount of gas pressure between the output face 36 and the surface of the substrate 20, the apparatus of the present invention provides at least some portions of air support for the delivery head 10 itself or alternatively to the substrate 20, or more suitably a gas fluid support. . This configuration helps to simplify the transmission requirements of the delivery head 10 as described later. The effect of allowing the delivery head to access the substrate such that it is supported by gas pressure helps to provide separation between the gas streams. By allowing the delivery head to float here On the gas stream, a pressure field is established in the region of the reactive and purge gas stream which results in directing gas from the inlet to the exhaust port with little or no mixing of other gas streams. In this device, the close proximity of the coating head to the substrate results in a relatively high pressure and pressure height variation beneath the coating head. The absence of a gas diffuser system within the distribution head or insufficient gas diffusion system will indicate a very small pressure drop in the gas flowing within the distribution head. In this case, if the random force causes a small increase in the gap on one side of the distribution head, the pressure in the region can be lowered and the gas can flow into the region at an excessively high ratio. In contrast, when using the diffuser system according to the present invention, most of the pressure drop occurs within the delivery head such that the gas flowing from the delivery head remains relatively uniform regardless of any potential changes below the delivery head.

In one such embodiment, because the spacing D is relatively small, even a small change in distance D (e.g., even 100 microns) requires a significant change in flow rate and thus gas pressure at spacing D. For example, in one embodiment, a doubling of the spacing D involving a variation of less than 1 mm would require a gas flow rate that provides a spacing D to be more than doubled, preferably more than four times. As a general principle, it is more advantageous to consider implementing a solution that minimizes the spacing D and therefore operates at a reduced flow rate.

However, the present invention does not require a floating delivery head system, and the delivery head and substrate can be generally at a fixed distance D as in conventional systems. For example, the delivery head and substrate can be mechanically secured at a distance from one another, wherein the delivery head is incapable of moving vertically relative to the substrate in response to changes in flow rate and wherein the substrate is on a vertically fixed substrate carrier.

In an embodiment, there is provided for providing a gaseous material for advancement on a substrate The conveying device for the output surface of the film material deposition comprises:

(a) a plurality of air inlets including at least a first air inlet, a second air inlet, and a third air intake capable of respectively receiving a common supply of the first gaseous material, the second gaseous material, and the third gaseous material And (b) at least three sets of extended jet channels, the first set comprising one or more first extended jet channels, the second set comprising one or more second extended jet channels, and the third set comprising at least two a third extended injection passage, each of the first, second, and third extended injection passages being in fluid communication with one of the respective first, second, and third intake ports; Each of the first extended injection passages is separated from the nearest second extended injection passage by at least one extended side thereof; wherein each of the first extended injection passages and each of the second extended injection passages is located between the third extended injection passages Wherein each of the first, second and third extended jet channels is elongated in length and substantially parallel; wherein each of the three sets of extended jet channels extends in each of the extended jet channels Jet pass The flow of at least one of the first gaseous material, the second gaseous material, and the third gaseous material can be directed substantially at right angles to the surface of the substrate at a right angle to the output face of the delivery device, the gaseous material The flow can be provided directly or indirectly from each of the at least one set of extended spray channels; and wherein at least a portion of the delivery device is formed as a plurality of apertured plates that overlap to define interconnecting the supply and guide channels Networking for each of the first gaseous material, the second gaseous material, and the third gaseous material They are delivered from their respective intake ports to their respective extended injection channels.

For example, the first and second gaseous materials can be mutually reactive gases, and the third gaseous material can be a purge gas.

The exploded view of Figure 4 shows how a delivery head 10 can be constructed from a set of perforated plates for a small portion of the overall assembly in one embodiment, and an exemplary gas flow path for only a portion of a gas is shown. The web 100 of the delivery head 10 has a series of input ports 104 for connection to a gas supply located upstream of the delivery head 10 and not shown in FIG. Each input port 104 is in communication with a pilot chamber 102 that directs the received gas downstream to the gas chamber plate 110. The gas chamber plate 110 has a supply chamber 112 in fluid communication with individual guide channels 122 on the gas guide plate 120. Airflow travels from the guide passage 122 to a particular extended exhaust passage 134 on the floor 130. The gas diffuser unit 140 provides diffusion and final delivery of the input gas at its output face 36. The exemplary airflow F1 is tracked through each of the component assemblies of the delivery head 10. In the present application, the x-y-z axis orientation shown in Figure 4 also applies to Figures 5A and 7.

As shown in the example of FIG. 4, the transport assembly 150 of the delivery head 10 is formed as a configuration in which an orifice plate is overlapped as follows: a connection plate 100, a gas chamber plate 110, a gas guide plate 120, and a bottom plate 130. In this "horizontal" embodiment, the plates are disposed generally parallel to the output face 36. As described later, the gas diffuser unit 140 may also be formed by overlapping orifice plates. It can be appreciated that any of the panels shown in Figure 4 can be fabricated from a stack of overlapping panels themselves. For example, it may be advantageous to form the web 100 from four or five stacked orifice plates that are suitably coupled together. Compared to the machining or molding methods that form the guiding chamber 102 and the input port 104, such The configuration may not be too complicated.

As indicated above, the transport device for depositing film material on the substrate comprises a gas diffuser, wherein at least one of the plurality of extension channels from the first, second and third extended jet channels (preferably all three) The gaseous material can pass through the gas diffuser before being transported from the transport device to the substrate (including deposited on the substrate), wherein the transport device allows each gaseous material to pass sequentially through the respective inlet, the extended jet channel, and (relative to the At least one plurality of jet channels) a gas diffuser. A gas diffuser may be in the at least one plurality of jet extension channels and/or upstream of the jet extension channels.

In an advantageous embodiment, the gas diffuser is capable of providing a coefficient of friction greater than 1 x 10 ² , preferably from 1 x 10 ⁴ to 1 x 10 ⁸ , more preferably from 1 x 10 ⁵ to 5 x 10 ⁶ . This provides counter pressure and promotes pressure balance where the flow of at least one of the first, second, and third gaseous materials exits the delivery device.

This coefficient of friction assumes that the feature area in the equation below is equal to the total area between the discharge extension channels on either side of each of the at least one plurality of jet extension channels. In other words, the area is defined by the line connecting the ends of the respective discharge extension channels. For the purpose of the device request, this coefficient of friction also assumes that the representative gas is nitrogen at 25 ° C and the average velocity is between 0.01 and 0.5 m/sec in order to calculate the coefficient of friction for the device independently of the method of use. The average speed is calculated based on the flow rate divided by the feature area A defined below. (These representative values are used to characterize the delivery device independently of the method of use and are not suitable for use in the process according to the invention, the actual values being applicable in the process of the invention.)

The term "coefficient of friction" can be explained as follows. Attribution when the airflow passes through the channel In the resistive nature of the diffuser, the pressure on the upstream side of the diffuser will be higher than the pressure present on the downstream side. The pressure difference in the diffuser is called the pressure drop.

A gas diffuser (which may be a device, a material, or a combination thereof) in accordance with the present invention provides flow resistance in the passage while still allowing fluid to be uniformly transferred. A gas diffuser member such as that used in the present invention is placed at the end of a flow path of a certain shape. In the absence of a gas diffuser, the fluid can exit the channel at any point and will unconditionally exit unrestricted. In the presence of a gas diffuser, the fluid traveling until the gas diffuser will encounter strong resistance there and will travel along all areas of the diffuser via the path of least resistance to substantially more uniformly retreat.

Since the primary property of gas diffusers is their resistance to flow, it is convenient to characterize this resistance by accepted methods in the field of fluid dynamics. (Transport Phenomena, RB Bird, WE Stewart, EN Lightfoot, John Wiley & Sons, 1960). The pressure drop in the diffuser can be characterized by the coefficient of friction f provided by the gas diffuser:

Where F _k is the force applied due to fluid flow, which is ultimately related to pressure drop; A is the characteristic area; and K is the kinetic energy of the fluid flow. The diffuser can take many shapes. For a typical system as described in relation to the present invention, A is placed perpendicular to the output stream and _Fk is placed parallel to the output stream. Therefore, the term F _k /A can be regarded as the pressure drop ΔP caused by the gas diffuser.

The kinetic energy of the flow is:

Where ρ is the gas density and <v> is the average velocity, which is equal to the flow rate of the gaseous material divided by the characteristic area A. (The density of nitrogen can be used as a first approximation of the gas actually used in the process, or as a representative gas for characterizing the delivery head device.) Therefore, the pressure drop due to the gas diffuser can be summarized as:

Equation (6) can be used to calculate the coefficient of friction f (number of times without cause) because other coefficients can be experimentally determined or measured as shown in the examples below.

Materials or devices that exhibit a higher coefficient of friction provide higher resistance to airflow. The coefficient of friction of a given diffuser can be measured by placing the diffuser in a channel while recording the pressure drop and the flow rate of the gas presented to the diffuser. Depending on the gas flow rate and the shape of the channel being learned, the velocity v can be calculated, thus allowing the friction coefficient to be calculated from the above equation. The coefficient of friction of a given system is not completely constant, but rather has a relatively weak dependence on the flow rate. For practical purposes, it is important to know the coefficient of friction only at the typical flow rates used in a given system or method. Regardless of the method, for the head device, the average speed <v> can be regarded as 0.01 to 0.5 m/sec, which is a representative value. (The coefficient of friction claimed in the case of equipment should satisfy all average distances <v> in this representative range.)

A suitable gas diffuser can provide a coefficient of friction of greater than 1 x 10 ² , preferably from 1 x 10 ⁴ to 1 x 10 ⁸ , more preferably from 1 x 10 ⁵ to 5 x 10 ⁶ for the gas stream passing through the gas diffuser. This provides the desired back pressure and promotes pressure balance where the gas stream of at least one of the first, second and third gaseous materials, preferably all three gaseous materials, exits the delivery device through the gas diffuser.

As indicated above, the characteristic area A of the average velocity <v> of the equation (6) is determined to be equal to the total between the discharge extension channels on either side of the respective jet extension channels in the jet extension channel in fluid communication with the gas diffuser. area. In other words, the area is defined by the line connecting the two ends of the respective discharge extension channels. For the purposes of the equipment request, this also assumes that the representative gas is nitrogen at 25 °C.

Those skilled in the art will appreciate that a typical random material alone will not provide the necessary coefficient of friction. For example, while stainless steel perforated screens provide relatively small features for generally machined or mechanically fabricated components, they can exhibit a coefficient of friction that is too low to be sufficient for use in the gas diffuser of the present invention, such as Shown in the examples below.

For the purpose of determining the coefficient of friction, in most cases, since the effect of the flow path leading to the gas diffuser is relatively small, a good approximation can be obtained by using the pressure entering the delivery head.

The gas diffuser can be, for example, a mechanically formed device that provides the necessary coefficient of friction, wherein the jet extension channel is designed to pass the first, second, and third gaseous materials after passing through the gas diffuser element containing the opening in the solid material Provided indirectly to the substrate. For example, the solid material can be steel and the openings formed by molding, machining, applying electro-radiation or lithography, or the like.

Alternatively, the gas diffuser can comprise a porous material. Instead of machining the holes in the solid material, a porous material with micropores can be used to create the desired back pressure. The uniform distribution of the intake air allows for improved uniformity of deposition growth and For some embodiments it results in a good float of the floating head. The porous material facilitates the provision of relatively simple units that avoid the difficulty of machining steel and the like.

In the literature, porous materials have been used to form the back pressure of the air bearing, but such applications do not involve cross flow (i.e., laterally moving gases). Thus, sintered alumina particles can be used to form a film for air support. However, in a preferred embodiment of the ALD system of the present invention, the gas preferably flows substantially vertically from the outlet while minimizing or eliminating the undesirable side motion of the gas mixture. It is therefore particularly desirable and advantageous to have a porous material with a generally vertical tubular opening or aperture to direct the gas flow.

Porous materials have also been used in filters where the purpose is to keep one component of the stream on one side while allowing the other component to pass through. In contrast, in the present invention, the aim is a medium resistance to the flow of the entire gaseous material. For this purpose, two preferred classes of porous materials are as follows:

The first preferred class of porous materials comprises a porous material having a uniform controlled diameter, columnar type pore structure. In a film (or layer) made of the material, the flow through the film is generally unidirectional, with substantially no cross flow between the pore channels. The alumina formed by the high-purity aluminum anode treatment is well known in the literature for its uniformity of pore diameter (although the cross-sectional shape of the pores is not necessarily circular or regular), and the materials may be 0.02, 0.1. And 0.2 micron diameter is available. The pores in ANOPORE alumina (commercially available alumina) are quite dense, 1.23 x ¹⁰⁹ pores per square centimeter (J Chem Phys, Vol. 96, p. 7789, 1992). However, a variety of pore diameters and inter-pore distances can be made. The porous material can also be formed from titanium oxide, zirconium oxide and tin oxide (Adv. Materials, Vol. 13, p. 180, 2001). Another commercially available material having a cylindrical pore is a Polycarbonate Track Etch (PCTE) film made of a thin microporous polycarbonate film material called NUCLEOPORE. Block copolymers can be formed into similar configurations due to various tuning capabilities.

Thus, in a preferred embodiment, the gas diffuser comprises a porous material such as anodized aluminum comprising an isolated non-attached pore structure wherein the pores are substantially perpendicular to the surface.

In all such materials, the precise range of pore diameters and the density of pores (or pore volume) should be adjusted to achieve the appropriate coefficient of friction for the desired flow. It is necessary to avoid the reactivity of the diffusion membrane with the flowing gas. For example, for inorganic oxides, this situation may not pose a potential problem compared to organic based materials.

In addition, the film should have some mechanical toughness. The flowing gas will exert pressure on the membrane. Toughness can be achieved with a support film to create a coefficient of friction by a layer of smaller pores coupled to a more stable layer having larger pores.

In a second preferred class of porous materials, the porous material is fabricated such that the flow can be isotropic, i.e., laterally within the film and through the film. For the purposes of the present invention, however, the isotropically flowing material is preferably separated by walls (e.g., ribs) on the non-porous material that will direct the gaseous material in each of the output channels to the gaseous state in the other output channels. The material is isolated and prevents the gaseous materials from mixing with one another in the gas diffuser or when exiting the gas diffuser or delivery head. For example, the porous materials may be sintered from small organic or inorganic particles Come. Sintering typically involves applying heat and/or pressure sufficient to bond the particles, preferably both. A variety of such porous materials are commercially available, such as porous glass (VYCOR has a void volume of, for example, 28%) and porous ceramics. Alternatively, the fibrous material can be extruded to form a tight network that limits or resists gas flow. Alternatively, the porous stainless steel can be formed by plasma coating on a subsequently removed substrate.

In one embodiment, to produce a suitable back pressure while still providing relative separation between the gas channels, a polymeric material that is treated in a manner that produces suitable pores, such as TEFLON materials that are treated to produce porosity, can be used (GoreTex, Inc. Newark, Delaware). In this case, the pores may not be interconnected. The natural chemical inertness of such materials is also advantageous.

For porous materials comprising pores formed by gaps between the particles, the pores are interconnected voids formed by a hole forming agent or other means in the solid material, or the pores are formed of micron- or nano-sized fibers. For example, the porous material can be formed by a gap between inorganic or organic particles that are bonded together by sintering, by pressure and/or heat, adhesion materials, or other bonding methods. Alternatively, the porous material can be obtained by processing a polymeric film to create porosity.

In a preferred embodiment, the gas diffuser comprises a porous material comprising an average diameter of less than 10,000 nm, preferably from 10 to 5000 nm, more preferably an average diameter of 50, as determined by mercury immersion porosimetry. 5,000 nm pores.

Various configurations of porous materials in gas diffusers are possible. For example, the porous material may comprise one or more layers of different porous materials, or be porous or The porous material layer supported by the perforated sheet, the layers being separated by spacer elements as appropriate. Preferably, the porous material comprises a layer having a thickness of from 5 to 1000 microns, preferably from 5 to 100 microns, such as 60 microns. In one embodiment, the porous material is in the form of at least one horizontal placement layer that covers an end face of the delivery assembly and that forms part of a delivery device through which the gaseous material exits the output face.

The porous material can form a continuous layer that optionally has a pathway formed therein mechanically. For example, the porous layer of the gas diffuser can comprise a mechanically formed opening or extension channel for venting the gaseous material back through the delivery device with relatively unimpeded access. Alternatively, the layer of porous material can be in the form of a substantially completely continuous sheet in a stack of sheets.

In another embodiment, the porous material can be introduced or formed in the extended spray channel or from other walled channels in the flow path extending the spray channel, for example by adhering or sintering the particles introduced into the channel. The channel can be at least partially filled with a porous material. For example, the diffuser element or portion thereof may be formed from an extended passage in the steel sheet where the particles are introduced and subsequently sintered.

Thus, the gas diffuser can be a component assembly in which the porous material is held in a separate closed zone. For example, a porous alumina material can be grown on a previously machined aluminum article such that the resulting porous structure has a larger opening for the purge passage and a sheet having vertical voids for supplying the gas.

Figures 5A through 5D show the major components assembled together to form the delivery head 10 of the embodiment of Figure 4. FIG. 5A is a perspective view showing the web 100 of the plurality of guiding chambers 102. FIG. 5B is a plan view of the gas chamber panel 110. In an embodiment, the supply chamber 113 is used to deliver the purge or inert gas of the head 10. In an embodiment, the supply chamber 115 provides a mixture of precursor gases (O); The exhaust chamber 116 provides an exhaust path for this reactive gas. Similarly, supply chamber 112 provides another desired reactive gas, i.e., a second reactive gaseous material (M); exhaust chamber 114 provides an exhaust path for this gas.

Figure 5C is a plan view of the gas guide plate 120 of the delivery head 10 in this embodiment. A plurality of guide channels 122 of the second reactive gaseous material (M) will be provided to connect the mode configuration of the appropriate supply chamber 112 to the bottom plate 130. The respective exhaust guide passage 123 is positioned adjacent to the guide passage 122. The guide channel 90 provides a first reactive gaseous material (O) and has a corresponding exhaust gas guiding passage 91. The guide channel 92 provides a third inert gaseous material (I). It should be emphasized again that Figures 4 and 5A-5D show an illustrative embodiment; numerous other embodiments are also possible.

FIG. 5D is a top plan view of the bottom plate 130 of the delivery head 10. The bottom plate 130 has a plurality of extended spray passages 132 that are interleaved with the extended exhaust passages 134. Therefore, in this embodiment, there are at least two extended second injection passages and each of the first extended injection passages has a first extended exhaust passage and a second third extended injection passage and a nearest second extended injection on its two extended sides. The channels are separated. More specifically, there are a plurality of second extended injection channels and a plurality of first extended injection channels; wherein each of the first extended injection channels is extended on the two extended sides thereof by the first extended exhaust passage and the third extended extended injection passage and the nearest The second extended jet channels are separated; and wherein each of the second extended jet channels is separated on its two extended sides by a first extended exhaust channel and a second, third extended jet channel thereof from the nearest first extended jet channel. Obviously, the delivery device can still include a first or second extended spray channel at each of the two ends of the delivery head, the delivery head being at the edge closest to the output face of the delivery device (above Figure 5D) Edge and bottom edge) does not have a second or first extended jet Road.

FIG. 6 is a perspective view showing the bottom plate 130 formed of a horizontal plate and showing the input port 104. The perspective view of FIG. 6 shows the outer surface of the bottom plate 130 as viewed from the output side and having an extended spray passage 132 and an extended exhaust passage 134. Referring to Figure 4, the view of Figure 6 is taken from the side facing the direction of the substrate.

The exploded view of Fig. 7 shows the basic configuration of the components used to form one embodiment of the mechanical gas diffuser unit 140 for the embodiment of Fig. 4 and other embodiments described later. These components include a nozzle plate 142, which is shown in the plan view of Figure 8A. As shown in the plan view of FIG. 8A, the nozzle plate 142 is placed against the bottom plate 130 and obtains its air flow from the extended injection passage 132. In the illustrated embodiment, the first diffuser output passage 143 in the form of a nozzle orifice provides the desired gaseous material. The slot 180 is provided in an exhaust path as will be described later.

The gas diffuser plate 146, which is shown in Fig. 8B and which cooperates with the nozzle plate 142 and the face plate 148, is placed against the nozzle plate 142. The configuration of the various passages on nozzle plate 142, gas diffuser plate 146, and panel 148 is optimized to provide the desired amount of gas flow diffusion while effectively directing the exhaust gases away from the surface area of substrate 20. The slot 182 provides an exhaust port. In the illustrated embodiment, the gas supply slots and exhaust slots 182 that form the second diffuser output passage 147 alternate in the gas diffuser plate 146.

Panel 148, as shown in Figure 8C, faces substrate 20. In this embodiment, the third diffuser passage 149 providing the gas and the exhaust slot 184 are also alternately present.

Figure 8D focuses on the gas delivery path through the gas diffuser unit 140; Figure 8E shows the exhaust path in a corresponding manner. Referring to Figure 8D, for a representative set of air vents, an overall configuration for sufficiently diffusing the reactive gas of output stream F2 in one embodiment is shown. Gas from the bottom plate 130 (Fig. 4) is provided via a first diffuser passage 143 on the nozzle plate 142. The gas passes downstream to the second diffuser passage 147 on the gas diffuser plate 146. As shown in Figure 8D, there may be a vertical offset between the vias 143 and 147 in one embodiment (i.e., using the horizontal plate configuration shown in Figure 7, the vertical is normal relative to the plane of the horizontal plate) ), which contributes to counter-pressure and thus contributes to a more uniform flow. The gas then proceeds further downstream to the third diffuser passage 149 on the face plate 148 to provide an output passage 12. The different diffuser passages 143, 147, and 149 may not only be spatially offset, but may also have different geometries to promote intermolecular mixing and homogeneous diffusion of the gaseous material as it flows through the delivery head.

In the particular case of the configuration of Figure 8D, most of the back pressure is created by the nozzle holes that form the passages 143. If the gas is directed to the substrate in the absence of subsequent vias 147 and 149, the high velocity of the gas exiting the nozzle orifice may result in non-uniformity. Thus passages 147 and 149 help to improve the uniformity of the gas flow. Alternatively, the coating apparatus can operate only with a nozzle-based back pressure generator, thereby eliminating passages 147 and 149 at the expense of slight coating non-uniformity.

The nozzle holes in the nozzle plate 142 can have any size suitable for creating a back pressure. The average diameter of the holes is preferably less than 200 microns, more preferably less than 100 microns. In addition, the use of holes in the back pressure generator is convenient and not necessary. As long as the size is selected to provide the required back pressure, the back pressure can also be He produces geometric shapes such as gaps.

Figure 8E depicts, in a symbolic manner, an exhaust path provided for gas evolution in a similar embodiment, wherein the downstream direction is opposite to the downstream direction of the supply gas. Flow F3 indicates the path of the evolved gases passing through successive third, second, and first exhaust slots 184, 182, and 180, respectively. Unlike the more tortuous mixing path for the gas supply stream F2, the venting configuration shown in Figure 8E is intended to rapidly move the exhaust from the surface. Therefore, the flow F3 is relatively straight, which allows the gas to be released away from the surface of the substrate.

Thus, in the embodiment of FIG. 7, gaseous materials from each of the first, second, and third extended injection passages 132 that extend the injection passages can pass through the gas diffuser unit 140, respectively, before being transported from the delivery device to the substrate. Wherein the delivery means allows each gaseous material to pass sequentially through the respective inlet, the extended injection passage and the gas diffuser unit 140. The gas diffuser unit in this embodiment is a gas diffuser member for each of the three gaseous materials, although a diffuser element that does not form a separate or isolated split of the common assembly can be used. The diffuser element can also be associated with or placed in the exhaust passage.

Also in this embodiment, the gas diffuser unit 140 is a unit that is designed to be separable from the remainder of the delivery head 150 and generally covers the first of the delivery devices prior to the gas diffuser element. The final opening or flow path of the second and third gaseous materials. Thus, the gas diffuser unit 140 essentially provides a final flow path for the first, second, and third gaseous materials to be delivered to the substrate from the output face of the delivery device. However, the gas diffuser element can also be designed as an inseparable part of the delivery head.

In particular, the gas diffuser unit 140 of the embodiment of Figure 7 includes vertically stacked interconnecting passages in three vertically disposed gas diffuser assemblies (or plates) that provide a flow path for the gaseous material in combination. . The gas diffuser unit 140 provides two substantially vertical flow paths separated by a generally horizontal flow path, wherein each substantially vertical flow path is provided by extending one or more passages in the direction of extension in the two elements, and Wherein each substantially horizontal flow path is in a narrow space between parallel surface regions of two parallel gas diffuser assemblies. In this embodiment, the three substantially horizontally elongated diffuser assemblies are substantially flat stacked plates and are comprised of a central gas diffuser assembly (gas diffuser plate) positioned adjacent the parallel gas diffuser assembly nozzle plate 142 and the face plate 148. The thickness of 146) defines a relatively narrow space. However, the two plates of Figure 7 can be replaced with a single plate, with gas diffuser plate 146 and panel 148 being machined or otherwise formed as a single plate, for example. In this case, the single element or plate of the gas diffuser may have a plurality of passages, each passage being formed parallel to the surface of one of the plates in a vertical cross section parallel to the thickness of the plate taken by the associated extended injection passage. An extension passage of the surface of the plate that is integrally connected to a narrow vertical passage leading to the other surface of the plate near one end thereof. In other words, a single component can combine the second and third diffuser passages 147 and 149 of Figure 8D into a single component or plate.

Thus, the gas diffuser unit according to the present invention may be a multi-stage system comprising a series of at least two substantially horizontally elongated diffuser assemblies having mutually orthogonal directions with respect to the end faces of the conveying means (eg, stacked plates) Parallel surface facing. Generally, associated with each of the extended injection passages of the first, second, and third injection passages, the gas diffuser includes at least two Vertically stacked or overlapping passages in a vertically disposed gas diffuser plate that in combination provide a flow path for the gaseous material comprising two substantially vertical flow paths separated by a generally horizontal flow path, wherein each The vertical flow path is provided by extending one or more passages or passage assemblies in the direction of extension and wherein each substantially horizontal flow path is provided by a narrow space between parallel surface regions in the parallel plates, wherein the vertical fingers are relative to The orthogonal direction of the output face of the conveyor. The term component via refers to a via component that does not pass through the component from beginning to end, such as by combining the second and third diffuser vias 147 and 149 of FIG. 8D into a single component or board. Component access.

In the particular embodiment of Figure 7, the gas diffuser comprises three sets of vertically stacked passages in three vertically disposed gas diffuser plates, respectively, wherein the central gas diffuser plate is located between two parallel gas diffuser plates The thickness defines a relatively narrow space. Two of the three diffuser assemblies (sequential first and third diffuser assemblies) each include a passage extending in the direction of extension for transferring gaseous material, wherein the passage in the first diffuser assembly is relative to the third The corresponding (interconnect) path in the diffuser assembly is horizontally offset (in a direction perpendicular to the length of the extension direction). This offset (between path 143 and path 149) can be better seen in Figure 8D.

Additionally, the second gas diffuser assembly sequentially positioned between the first and third diffuser assemblies includes passages 147 each in the form of an extended central opening, each of the first and third diffuser assemblies The width of the passage is relatively wide so that the central opening is defined by the two extended sides and the first diffuser assembly and the first will be viewed when viewed from above the gas diffuser The interconnect path of the triple diffuser assembly is contained within its boundaries. Thus, the gas diffuser unit 140 is capable of substantially deflecting the flow of gaseous material delivered therethrough. Preferably, the deflection is at an angle of 45 to 135 degrees, preferably 90 degrees, such that the vertical flow is changed to a parallel flow relative to the output surface and/or the surface of the substrate. Thus, the gaseous material stream can pass substantially vertically through the passages in the first and third gas diffuser assemblies and generally horizontally in the second gas diffuser assembly.

In the embodiment of FIG. 7, each of the plurality of vias in the first gas diffuser assembly includes a series of holes or perforations extending along the extension line, wherein respective interconnect paths in the third diffuser assembly are extended A rectangular slot that is not square at the end. (Thus more than one of the first gas diffuser assemblies can be connected to a single passage in the subsequent gas diffuser assembly.)

Alternatively, as noted above, the gas diffuser can comprise a porous material, wherein the delivery device is designed such that each of the individual jet extension channels passes the gaseous material within the respective jet extension channel and/or each of the jet extension channels The upstream porous material is then indirectly provided to the substrate. Porous materials typically comprise pores formed by chemical transformation or present in naturally occurring porous materials.

Referring again to FIG. 4, a combination of components shown as connection plate 100, gas chamber plate 110, gas guide plate 120, and bottom plate 130 can be assembled to provide a delivery assembly 150. There may be alternative embodiments to the delivery assembly 150 that include a delivery assembly formed from a vertical, rather than horizontal, perforated plate using the peer-to-peer configuration of FIG.

The perforated plate for the delivery head 10 can be formed and coupled in a variety of ways Start. Advantageously, the orifice plate can be manufactured independently using known methods such as progressive die, molding, machining or stamping. The combination of perforated plates can be largely different from the combinations shown in the embodiments of Figures 4 and 9A-9B, which form the delivery head 10 in a number of plates, such as from 5 to 100 plates. Stainless steel is used in one embodiment and is advantageous for its resistance to chemicals and corrosion. Ceramic, glass or other durable materials may be suitable for forming some or all of the apertured sheets, depending on the application and the reactive gaseous materials used in the deposition process, but the apertured sheets are typically metallic.

For assembly, the perforated plates can be bonded together or by mechanical fasteners such as bolts, clips or screws. For sealing, the orifice plate may be topcoated with a suitable adhesive or a sealant material such as a vacuum grease. An epoxy resin such as a high temperature epoxy resin can be used as an adhesive. Adhesive properties of molten polymeric materials such as polytetrafluoroethylene (PTFE) or Teflon (TEFLON) have also been used to bond the overlapping orifice plates of the delivery head 10 together. In one embodiment, a PTFE coating is formed on each of the perforated plates for the delivery head 10. When the applied heat approaches the melting point of the PTFE material (nominally 327 ° C), the plates are stacked (overlapped) and pressed together. Subsequent heat and pressure combinations form the delivery head 10 from the coated apertured sheet. The coating material acts as an adhesive and sealant. Kapton and other polymeric materials are alternatively used as interstitial coating materials for adhesion.

As shown in Figures 4 and 9B, the perforated plates should be assembled together in a suitable sequence to form a network of interconnected supply and guide channels for delivering gaseous material to the output face 36. When assembled together, can be used to provide alignment pins or classes A profile-like configuration in which the apertures and slots in the aperture plate are configured to mate with such alignment features.

Referring to Figure 9A, an alternative configuration for using a transport assembly 150 that vertically stacks one of the vertical placement panels or overlaps the orifice panels relative to the output face 36, as shown in the bottom view (i.e., from the gas injection side view). For simplicity of illustration, the portion of the delivery assembly 150 shown in the "vertical" embodiment of FIG. 9A has two extended injection passages 152 and two extended exhaust passages 154. The vertical plate configuration of Figures 9A through 13C can be easily expanded to provide a plurality of spray extension channels and exhaust extension channels. In the case where the orifice plates are disposed perpendicularly to the plane of the output face 36 as in Figures 9A and 9B, each of the extended spray channels 152 has a side wall defined by a partition (shown in more detail later) and between The centered reactant plate is formed. The correct alignment of the pores then provides fluid communication with the gaseous material supply.

The exploded view of Figure 9B shows the configuration of an apertured plate used to form a small portion of the delivery assembly 150 shown in Figure 9A. Figure 9C is a plan view showing a transport assembly 150 having five channels for ejecting gas and formed using stacked orifice plates. Figures 10A through 13B then show various panels in plan view and perspective view. For simplicity, letter designation is provided for each type of perforated plate: separator S, purge P, reactant R, and exhaust E.

From left to right in Figure 9B is a spacer 160(S) alternately present between the plates for directing gas toward or away from the substrate, which is also shown in Figures 10A and 10B. Purification plate 162 (P) is shown in Figures 11A and 11B. Exhaust plate 164 (E) is shown in Figures 12A and 12B. Reactant plate 166 (R) is shown in Figures 13A and 13B. Figure 13C shows the result obtained by horizontally flipping the reactant plate 166 of Figure 12A. Reactant plate 166'; this alternative orientation can also be used for venting plate 164 as desired. When the perforated plates overlap, the apertures 168 in each of the plates are aligned, thus forming a conduit to enable gas to pass into the extended injection output passage 152 and the extended exhaust passage 154 via the delivery assembly 150 as described with reference to FIG. (The term "overlap" has its conventional meaning, in which elements are placed one on top of the other in such a way that portions of one element are aligned with corresponding portions of the other and their perimeters generally coincide.)

Returning to Figure 9B, only one portion of the delivery assembly 150 is shown. The board structure of this part can be represented by the previously assigned alphabetic abbreviation, ie: S-P-S-E-S-R-S-E-S

(where the last spacer in this sequence is not shown in Figure 9A or 9B.) As shown in this sequence, the spacer 160(S) defines the channels by forming sidewalls. The minimum delivery assembly 150 that provides both reactive gases for typical ALD deposition and the necessary purge gas and exhaust passages will be represented using a fully abbreviated sequence: SPS-E1-S-R1-S-E1-SPS -E2-S-R2-S-E2-SPS-E1-S-R1-S-E1-SPS-E2-S-R2-S-E2-SPS-E1-S-R1-S-E1-SPS

Wherein R1 and R2 represent reactant plates 166 in different orientations for the two different reactive gases used, and E1 and E2, respectively, represent exhaust plates 164 in different orientations.

The extended exhaust passage 154 need not be a vacuum orifice in the conventional sense, but may only be provided to extract the flow in its respective output passage 12, thus contributing to a uniform flow pattern within the passage. A negative extraction force that is only slightly less than the negative value of the gas pressure adjacent the extended injection channel 152 can contribute to the orderly flow move. The negative extraction force can be operated, for example, with an extraction pressure between 0.2 and 1.0 atmospheres at the source (e.g., a vacuum pump), while a typical vacuum is, for example, less than 0.1 atmosphere.

The use of the flow pattern provided by the delivery head 10 provides several advantages over conventional methods of separately pulsed delivery of gas to the deposition chamber, such as those previously mentioned in the background section. The mobility of the deposition apparatus is improved, and the apparatus of the present invention is suitable for high volume deposition applications where the substrate size exceeds the size of the deposition head. Fluid dynamics has also been improved over previous methods.

The flow configuration for use in the present invention allows for a very small distance D, preferably less than 1 mm, between the delivery head 10 and the substrate 20 as shown in FIG. The output face 36 can be positioned very close to the surface of the substrate by up to 1 mil (about 0.025 mm). Proximity positioning is facilitated by the pressure of the gas generated by the reactive gas stream. In contrast, CVD equipment requires significantly greater spacing. Previous methods such as those described in U.S. Patent No. 6,821,563, the entire disclosure of which is incorporated herein by reference to the entire entire entire entire entire entire entire entire entire disclosure Implemented at less than 0.450 mm. In fact, it is preferred to position the delivery head 10 closer to the surface of the substrate in the present invention. In a particularly preferred embodiment, the distance D from the surface of the substrate can be 0.20 mm or less, preferably less than 100 μm.

When a large number of plates are assembled in a stacked plate embodiment, it is desirable that the gas stream delivered to the substrate be uniform throughout the channels of all transport gas streams (I, M or O materials). This can be achieved by appropriately designing an orifice plate, such as having a precision machining in a portion of the flow pattern of each plate to deliver an output or row to each extension. The gas passage provides a choke with a reproducible pressure drop. In an embodiment, the output channel 12 exhibits substantially equal pressure within no more than 10% of the deviation along the length of the opening. Even higher tolerances can be provided, such as allowing deviations of no more than 5% or even as low as 2%.

Although a method of stacking orifice plates is particularly useful for constructing a delivery head, there are several other methods for establishing such applicable structures in alternative embodiments. For example, the device can be constructed by directly machining a metal block or a plurality of metal blocks that are bonded together. In addition, molding techniques involving internal mold features can be used as appreciated by those skilled in the art. The device can also be constructed using any of a number of stereo lithography techniques.

In one embodiment of the invention, the delivery head 10 of the present invention maintains a suitable spacing D (Fig. 1) between its output face 36 and the surface of the substrate 20 by using a floating system. Figure 14 shows certain considerations regarding the use of the pressure of the gas stream ejected from the delivery head 10 to maintain the distance D.

In Figure 14, a representative number of output channels 12 and exhaust channels 22 are shown. The pressure of the gas ejected from one or more of the output channels 12 produces the force indicated by the downward arrow in this figure. In order for this force to provide a suitable cushioning or "air" support (gas fluid support) effect to the delivery head 10, there should be sufficient load bearing area, i.e., a solid surface area along the output face 36 that can be in intimate contact with the substrate. The percentage of the load bearing area corresponds to the relative amount of effective area of the output face 36 under which the allowable gas pressure accumulates. In the simplest terms, the load bearing area can be calculated as the total area of the output face 36 minus the total surface area of the output passage 12 and the exhaust passage 22. This means that the total flow of the gas flow area of the output channel 12 having the width w1 or the exhaust channel 22 having the width w2 is excluded. The area should be as large as possible. In one embodiment, 95% of the load bearing area is provided. Other embodiments may use smaller bearing area values such as 85% or 75%. The adjustment of the gas flow rate can also be used to vary the separation or damping force and thus the distance D accordingly.

It will be appreciated that there will be advantages in providing a gas fluid support such that the delivery head 10 is substantially maintained at a distance D above the substrate 20. This will allow the delivery head 10 to use substantially frictionless movement of any suitable type of transport mechanism. The transfer head 10 is then "circled" over the surface of the substrate 20 as it is reciprocally conveyed during deposition of the material during the deposition of the material.

As shown in Figure 14, the delivery head 10 may be too heavy such that the downward gas force is not sufficient to maintain the desired spacing. In this case, an auxiliary lifting assembly such as a spring 170, magnet or other device can be used to supplement the lifting force. In other cases, the air flow may be high enough to cause the opposite problem such that unless additional force is applied, the delivery head 10 will be forced apart from the surface of the substrate 20 by a great distance. In this case, the spring 170 can be a compression spring that provides additional force required to maintain the distance D (downward relative to the configuration of Figure 14). Alternatively, the spring 170 can be a magnet that supplements the downward force, an elastomer spring, or some other device.

Alternatively, the delivery head 10 can be positioned relative to some other orientation of the substrate 20. For example, the substrate 20 can be supported by a gas fluid bearing effect to counter gravity such that the substrate 20 can move along the delivery head 10 during deposition. One embodiment using a gas fluid bearing effect to deposit on the substrate 20 is shown in FIG. 20, wherein the substrate 20 is buffered above the delivery head 10. The substrate 20 passes through the output face 36 of the delivery head 10 in the direction of the two-way arrow as shown mobile.

The alternative embodiment of Figure 21 shows a substrate 20 on a substrate carrier 74, such as a web carrier or roller, that moves in direction K between the delivery head 10 and the gas fluid support 98. In this case, air or another inert gas may be used alone. In this embodiment, the delivery head 10 has an air bearing effect and cooperates with the gas fluid support 98 to maintain a desired distance D between the output face 36 and the substrate 20. The gas fluid support 98 can direct the pressure using a stream F4 of inert gas or air or some other gaseous material. It should be noted that in the deposition system of the present invention, the substrate carrier or holder may be in contact with the substrate during deposition, which may be a member of the transfer substrate, such as a roller. Therefore, the insulation of the substrate to be processed is not a requirement of the system of the present invention.

As described in particular with respect to Figures 3A and 3B, the delivery head 10 needs to be moved relative to the surface of the substrate 20 to perform its deposition function. This relative movement may include many ways of moving either or both of the delivery head 10 and the substrate 20, such as by moving the device that provides the substrate carrier. Depending on the number of deposition cycles required, the movement may oscillate or reciprocate or may move continuously. Although the continuous process is preferred, the rotation of the substrate can also be used, especially in batch processes. The actuator can be coupled to a body such as a mechanically coupled delivery head. An alternating force such as changing the magnetic field may alternatively be used.

ALD typically requires multiple deposition cycles to establish a controlled film depth with each cycle. By using the designation of the previously given type of gaseous material, for example in a simple design, a single cycle can provide a primary coating of the first reactive gaseous material O and a primary coating of the second reactive gaseous material M.

The distance between the output channels of the O and M reactive gaseous materials is determined to be completed. The required distance for the reciprocating movement of each cycle. For example, the delivery head 10 of Figure 4 can have a nominal channel width of 0.1 吋 (2.54 mm) in the width direction between the reactive gas channel outlet and the adjacent purge channel outlet. Therefore, in order for the reciprocating motion (as used herein along the y-axis) to allow all regions of the same surface to undergo a full ALD cycle, a stroke of at least 0.4 吋 (10.2 mm) would be required. For this example, the region of the substrate 20 will be exposed to the first reactive gaseous material O and the second reactive gaseous material M, with this distance moved. Alternatively, the delivery head can be moved a greater distance for its stroke, even from one end of the substrate to the other. Under such conditions, the grown film can be exposed to ambient conditions during its growth period, thereby causing no harmful effects in many environments of use. In some cases, consideration of uniformity may require random measures of the amount of reciprocation in each cycle in order to reduce edge effects or accumulation at the end of the reciprocating motion.

The delivery head 10 can have an output channel 12 that is only sufficient to provide a single cycle. Alternatively, the delivery head 10 can have a multi-cycle configuration that enables it to cover a larger deposition area or enable it to perform its reciprocating motion over a distance that allows two or more deposition cycles in one travel of the reciprocating distance .

For example, in a particular application, each O-M cycle was found to form a layer of atomic diameter on the treated surface. Therefore, in this case, four cycles are required to form a uniform layer of one atomic diameter on the treated surface. Similarly, in this case, 40 cycles are required to form a uniform layer of 10 atomic diameters.

An advantage of the reciprocating motion of the delivery head 10 for use in the present invention is that it allows deposition on the substrate 20 having an area that exceeds the area of the output face 36. Figure 15 shows schematically This shows how to achieve this wider area coverage using a reciprocating motion such as by the y-axis as indicated by arrow A and a right or lateral movement relative to the x-axis and reciprocating motion. It should be emphasized again that the motion in the x or y direction as shown in FIG. 15 can be moved by the transport head 10 or by the movement of the substrate 20 having the substrate carrier 74 providing the movement or by the transport head 10 and the substrate 20. The movement of the two is achieved.

In Fig. 15, the direction of relative movement of the delivery head and the substrate, which may include the distribution manifold, is perpendicular to each other. It is also possible to make this relative motion parallel. In this case, the relative motion needs to have a non-zero frequency component representing the oscillation and a zero frequency component representing the displacement of the substrate. This combination can be achieved by a combination of oscillation and displacement of the delivery head on the fixed substrate; a combination of oscillation and substrate displacement relative to the fixed substrate delivery head; or wherein the oscillation and fixed motion are caused by the movement of both the delivery head and the substrate. Any combination provided.

Advantageously, the delivery head 10 can be manufactured in a smaller size than is possible with many types of deposition heads. For example, in one embodiment, the output channel 12 has a width w1 of 0.005 吋 (0.127 mm) and a length extending to 3 吋 (75 mm).

In a preferred embodiment, ALD can be performed at or near atmospheric pressure and at a wide range of ambient and substrate temperatures, preferably below 300 °C. It is preferred to have a relatively clean environment to minimize the possibility of contamination; however, when using the preferred embodiment of the apparatus of the present invention, there is no need to use full "clean room" conditions or inertness for good performance. A closed place for gas.

Figure 16 shows the environment for providing relatively good control and no contaminants An atomic layer deposition (ALD) system 60 of chamber 50. The gas supplies 28a, 28b, and 28c provide the first, second, and third gaseous materials to the delivery head 10 via a supply line 32. The optional use of the flexible supply line 32 facilitates the ease of movement of the delivery head 10. For simplicity, optional vacuum vapor recovery equipment and other carrier components are not shown in Figure 16 but may also be used. The transfer subsystem 54 provides a substrate carrier that transports the substrate 20 along the output face 36 of the delivery head 10, which provides movement in the x-direction using the coordinate axis system used in this disclosure. Motion control and overall control of valves and other support components can be provided by control logic processor 56, such as a computer or dedicated microprocessor assembly. In the configuration of FIG. 16, control logic processor 56 controls actuator 30 that provides reciprocating motion of delivery head 10 and transmission motor 52 that controls transmission subsystem 54. The actuator 30 can be any of a number of devices suitable for causing the delivery head 10 to reciprocate along the moving substrate 20 (or alternatively along the stationary substrate 20).

17 shows an alternate embodiment of an atomic layer deposition (ALD) system 70 for thin film deposition on a web substrate 66 that is transported through a delivery head 10 along a web conveyor 62 that acts as a substrate carrier. The web itself may be the substrate being processed or may provide support for the substrate (another web or a separate substrate, such as a wafer). The delivery head conveyor 64 conveys the delivery head 10 across the surface of the web substrate 66 in a direction transverse to the direction of travel of the web. In one embodiment, the delivery head 10 is urged to reciprocate across the surface of the web substrate 66 with a full separation force provided by the gas pressure. In another embodiment, the delivery head conveyor 64 uses a lead screw or similar mechanism that traverses the width of the web substrate 66. In another embodiment, a plurality of delivery heads 10 are used at suitable locations along the web conveyor 62.

Figure 18 shows another atomic layer deposition (ALD) system 70 in a web configuration that uses a fixed delivery head 10 in which the flow pattern is oriented at right angles to the configuration of Figure 17. In this configuration, the movement of the web conveyor 62 itself provides the movement required for ALD deposition. Reciprocating motion can also be used in this environment. Referring to Figure 19, an embodiment of a portion of the delivery head 10 is shown in which the output face 36 has a certain amount of curvature that may be advantageous for certain web coating applications. A convex curvature or a concave curvature can be provided.

In another embodiment that may be particularly suitable for web manufacturing, the ALD system 70 can have a plurality of delivery heads 10 or dual delivery heads 10 with a delivery device disposed on each side of the web substrate 66. A flexible delivery head 10 is alternatively provided. This will provide a deposition apparatus that exhibits at least some compliance with the deposited surface.

In another embodiment, one or more of the delivery channels 10 of the delivery head 10 may be configured using a lateral airflow, the configuration being disclosed in the previously cited application by Levy et al., filed on March 29, 2006, entitled "APPARATUS FOR ATOMIC LAYER DEPOSITION, "US Patent Application Serial No. 11/392,006. In this embodiment, the gas pressure that supports separation between the delivery head 10 and the substrate 20 can be maintained by a number of output channels 12, such as by the channels through which the purge gas is injected (the channel labeled I in Figures 2-3B). The lateral flow can then be used for one or more of the output channels 12 that inject reactive gases (the channels labeled O or M in Figures 2-3B).

An advantage of the apparatus of the present invention is its ability to perform deposition on a substrate over a wide range of temperatures, including room temperature or near room temperature in certain embodiments. The device of the invention can operate in a vacuum environment, but is particularly suitable Operates at atmospheric pressure or near atmospheric pressure.

A thin film transistor having a semiconductor thin film fabricated according to the method of the present invention can exhibit a field effect electron mobility of greater than 0.01 cm ² /Vs, preferably at least 0.1 cm ² /Vs, more preferably greater than 0.2 cm ² /Vs. Additionally, an n-channel thin film transistor having a semiconductor film fabricated in accordance with the present invention is capable of providing an on/off ratio of at least 10 ⁴ , advantageously at least 10 ⁵ . The on/off ratio is measured as the maximum/minimum value of the drain current when the gate voltage representing the associated voltage available on the gate line of the display rapidly changes from one value to another. In the case where the drain voltage is maintained at 30V, the typical value group is -10V to 40V.

While the air bearing effect can be used to at least partially separate the delivery head 10 from the surface of the substrate 20, the apparatus of the present invention can alternatively be used to lift or lift the substrate 20 from the output surface 36 of the delivery head 10. Other types of substrate holders may alternatively be used, including, for example, a platen.

Example 1

A mechanical gas diffusion element according to the embodiment of Figure 8D is constructed. In this element, a 130 micron thick nozzle plate contains 50 micron holes spaced 1000 microns apart. The mixing chamber consisted of another 130 micron thick plate with a 460 micron chamber opening. Finally, the gas exits via another 130 micron thick plate in which the 100 micron exit slot is cut.

The diffuser plate is mounted to the clamp so that the flow can be presented to the nozzle configuration. The cumulative flow area defined by the area between the exit slots in this setup is 9.03 x 10 ^-4 m ² . Nitrogen (density = 1.14 kg/m ³ ) having a total volume flow of 5.46 × 10 ^-5 m ³ /s was passed through the apparatus, resulting in a gas velocity of 0.06 m/s. Due to this gas velocity, a pressure drop of 2760 Pa across the diffuser was measured. Pressure was measured using a commercially available digital pressure transducer/meter (available from Omega). Since the definition of the coefficient of friction is related to the force exerted by the flow on the gas diffuser, the measured pressure drop is based on force/area and not directly on force. The coefficient of friction f is calculated to be 1.3 × 10 ⁶ .

According to the present invention, an Al ₂ O ₃ film is grown on a germanium wafer using an APALD device comprising the mechanical gas diffusion element according to the embodiment of FIG. The APALD unit is configured to have 11 output channels in the following configuration: Channel 1: Purified gas

Channel 2: oxidant-containing gas

Channel 3: purge gas

Channel 4: Gas containing metal precursor

Channel 5: purge gas

Channel 6: oxidant containing gas

Channel 7: purge gas

Channel 8: Gas containing metal precursor

Channel 9: purge gas

Channel 10: oxidant containing gas

Channel 11: purge gas

The film was grown at a substrate temperature of 150 °C. The gas stream delivered to the APALD coating head was as follows: (i) Nitrogen inert purge gas was supplied to channels 1, 3, 5, 7, 9, and 11 at a total flow rate of 3000 sccm.

(ii) A nitrogen-based gas stream containing trimethylaluminum is supplied to channels 4 and 8. This gas stream is obtained by mixing a stream of pure nitrogen of about 400 sccm at room temperature. A 3.5 sccm nitrogen stream filled with TMA was produced.

(iii) supplying a nitrogen-based gas stream containing water vapor to channels 2, 6, and 10. This gas stream was produced by mixing a stream of pure nitrogen of about 350 sccm at room temperature with a 20 sccm stream of nitrogen-filled nitrogen.

The coating head having the gas supply stream described above is brought close to the substrate and subsequently released such that it floats above the substrate based on the gas stream as previously described. At this time, the coating head was oscillated across the substrate for 300 cycles to produce an Al ₂ O ₃ film having a thickness of about 900 Å.

A leakage test structure was formed by coating an aluminum contact pad on the Al ₂ O ₃ layer using a mask during aluminum evaporation. This process results in the formation of an aluminum contact pad having an area of about 500 A and an area of 500 microns x 200 microns on Al ₂ O ₃ .

Leakage of the germanium wafer to the A1 contact surface is measured by applying a 20V potential between a given aluminum contact pad to the germanium wafer and measuring the amount of current with the HP-4155C® parametric analyzer. At a potential of 20 V, the leakage through the Al ₂ O ₃ dielectric was 1.3 × 10 ^-11 A. As can be seen from this test data, the coating head of this example produced a film with significantly lower leakage which was required to make a suitable dielectric film.

Example 2

Instead of the mechanical gas diffusion element of Example 1, a porous alumina membrane of 0.2 micron pores may be used. Commercially available porous alumina membranes containing 0.2 micron pores were purchased from Whatman Incorporated. The effective area of the membrane was 19 mm in diameter and mounted on a pressure filter holder through which nitrogen was passed at room temperature. The cumulative flow area defined by the area of the 19 mm diameter ring in this setup is 2.83 x 10 ^-4 m ² . Nitrogen (density = 1.14 kg/m ³ ) having a total volume flow of 1.82 × 10 ⁵ m ³ /s was passed through the apparatus, resulting in a gas velocity of 0.06 m/s. Due to this gas velocity, a pressure drop across the diffuser of 22690 Pa was measured. The coefficient of friction f is calculated to be 9.6 x 10 ⁶ .

Example 3

Instead of the mechanical gas diffusion element of Example 1, a porous alumina film of 0.02 micron pores may be used. Commercially available porous alumina membranes containing 0.02 micron pores were purchased from Whatman Incorporated. The effective area of the membrane was 19 mm in diameter and mounted on a pressure filter holder through which gas was passed at room temperature. The cumulative flow area defined by the area of the 19 mm diameter ring in this setup is 2.83 x 10 ^-4 m ² . Nitrogen (density = 1.14 kg/m ³ ) having a total volume flow of 1.82 × 10 ⁵ m ³ /s was passed through the apparatus, resulting in a gas velocity of 0.06 m/s. Due to this gas velocity, a pressure drop of 54830 Pa across the panel was measured. The coefficient of friction f is calculated to be 2.3 × 10 ⁷ .

Comparative example 4

Instead of the mechanical gas diffusion element of Example 1, the coefficient of friction of a metal screen having a 150 micron perforation was measured. Commercially available metal filters are available from McMaster Carr. The screen has a thickness of 250 microns and has a circular perforation of 150 microns. The perforations are in a hexagonal pattern with a 300 micron spacing at the center. This screen represents a relatively small pore size of a commercially available metal screen.

A screen is mounted on the holder so that the gas penetration through the filter is measured as a square cross-section of 1.5 mm x 2.3 mm. Nitrogen (density = 1.14 kg/m ³ ) with a total volume flow of 1.82 x 10 ^-5 m ³ /s was passed through the apparatus, resulting in a gas velocity of 5.27 m/s. Due to this gas velocity, a pressure drop of 480 Pa across the screen was measured. The coefficient of friction f was calculated to be 3.0 × 10 ¹ .

A higher velocity airflow is used for this measurement due to the extremely low coefficient of friction of the screen and the need for high gas velocities to produce a measurable pressure drop. Although this screen has a design that should provide some resistance to flow, the low coefficient of friction produced by this screen indicates that the screen itself cannot provide a coefficient of friction greater than 1 x 10 ² .

10‧‧‧ delivery head

12‧‧‧Output channel

14, 16, 18‧‧‧ intake duct

20‧‧‧Substrate

22‧‧‧Exhaust passage

24‧‧‧Exhaust duct

28a, 28b, 28c‧‧‧ gas supplies

30‧‧‧Actuator

32‧‧‧Supply line

36‧‧‧ Output surface

50‧‧‧ chamber

52‧‧‧Transporter motor

54‧‧‧Transporter subsystem

56‧‧‧Control logic processor

60‧‧‧Atomic Layer Deposition (ALD) System

62‧‧‧ web conveyor

64‧‧‧Transport head conveyor

66‧‧‧ web substrate

70‧‧‧Atomic Layer Deposition (ALD) System

74‧‧‧Substrate carrier

90‧‧‧ Guide channel for precursor materials

91‧‧‧Exhaust guide channel

92‧‧‧Gas gas guiding channel

96‧‧‧Substrate carrier

98‧‧‧ gas support

100‧‧‧Connecting plate

102‧‧‧Guiding chamber

104‧‧‧ input port

110‧‧‧ gas chamber plate

112, 113, 115‧‧‧ supply chamber

114, 116‧‧‧ exhaust chamber

120‧‧‧ gas guide plate

122‧‧‧ Guide channel for precursor materials

123‧‧‧Exhaust guide channel

130‧‧‧floor

132‧‧‧Extended jet channel

134‧‧‧Extended exhaust passage

140‧‧‧Gas diffuser unit

142‧‧‧Nozzle plate

143, 147, 149‧‧‧ first, second and third diffuser pathways

146‧‧‧ gas diffuser plate

148‧‧‧ panel

150‧‧‧Transport assembly

152‧‧‧Extended jet channel

154‧‧‧Extended exhaust passage

160‧‧ ‧ partition

162‧‧‧purification board

164‧‧‧Exhaust plate

166, 166'‧‧‧Reaction plates

168‧‧‧ pores

170‧‧‧ Spring

180‧‧‧Sequential first exhaust slot

182‧‧‧Sequential second exhaust slot

184‧‧‧Sequential third exhaust slot

A‧‧‧ arrow

D‧‧‧Distance

E‧‧‧Exhaust plate

F1, F2, F3, F4‧‧‧ airflow

I‧‧‧ third inert gaseous material

K‧‧ Direction

M‧‧‧Second reactive gaseous material

O‧‧‧First reactive gaseous material

P‧‧‧Purification board

R‧‧‧Reaction board

S‧‧‧Baffle

W1, w2‧‧‧ channel width

X‧‧‧ arrow

1 is a cross-sectional side view of one embodiment of a distribution manifold for atomic layer deposition in accordance with the present invention; and FIG. 2 is a cross-sectional side view of one embodiment of a delivery head, shown for supply to a substrate subjected to thin film deposition. An exemplary configuration of a gaseous material; Figures 3A and 3B are cross-sectional side views of one embodiment of a distribution manifold, schematically showing the accompanying deposition operation; Figure 4 is a deposition system in accordance with one embodiment of the present invention. Figure 5A is a perspective view of the connecting plate of the conveying head of Figure 4; Figure 5B is a plan view of the gas chamber plate of the conveying head of Figure 4; Figure 5C is a plan view of the gas chamber plate of Figure 4; Figure 5D is a plan view of the bottom plate of the delivery head of Figure 4; Figure 6 is a perspective view showing the bottom plate on the delivery head in an embodiment; Figure 7 is a gas diffuser according to one embodiment 8A is a plan view of a nozzle plate of the gas diffuser unit of FIG. 7; FIG. 8B is a plan view of the gas diffuser plate of the gas diffuser unit of FIG. 7; and FIG. 8C is a gas diffuser unit of FIG. surface A plan view; a perspective view of the mixed gas of the gas diffuser of FIG. 7 within the unit of Figure 8D; Figure 8E is a perspective view of a gas venting path using the gas diffuser unit of Figure 7; Figure 9A is a perspective view of a portion of the delivery head in an embodiment using a vertically stacked plate; Figure 9B is a delivery head shown in Figure 9A Figure 9C is a plan view showing a transport assembly formed using stacked plates; Figures 10A and 10B are plan and perspective views, respectively, of the spacer used in the vertical plate embodiment of Figure 9A; Figures 11A and 11B 1A and 12B are respectively a plan view and a perspective view of a venting plate used in the embodiment of the vertical plate of FIG. 9A; FIG. 13A and FIG. 13A are respectively a plan view and a perspective view of a venting plate used in the embodiment of the vertical plate of FIG. 9A; 13B is a plan view and a perspective view, respectively, of the reactant plate used in the embodiment of the vertical plate of FIG. 9A; FIG. 13C is a plan view of the reactant plate in an alternate orientation; FIG. 14 is a view showing a floating head and exhibiting a relevant distance dimension and Side view of one embodiment of a force direction deposition system; Figure 15 is a perspective view showing a dispensing head for use with a substrate transport system; Figure 16 is a perspective view showing a deposition system using the delivery head of the present invention; exhibition Perspective view of a deposition system applied to a mobile web of the embodiment; FIG. 18 is a perspective view showing another embodiment is applied to a mobile web of the deposition system; Figure 19 is a cross-sectional side view of one embodiment of a delivery head having an output face having a curvature; Figure 20 is a perspective view of an embodiment using gas buffer to separate the delivery head from the substrate; and Figure 21 is a view showing the inclusion and movement A side view of an embodiment of a deposition system for gas fluid support for use with a substrate.

10‧‧‧ delivery head

12‧‧‧Output channel

14, 16, 18‧‧‧ intake duct

20‧‧‧Substrate

22‧‧‧Exhaust passage

24‧‧‧Exhaust duct

36‧‧‧ Output surface

96‧‧‧Substrate carrier

A‧‧‧ arrow

D‧‧‧Distance

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Claims (64)

A conveying device for depositing a thin film material on a substrate, comprising: (a) a plurality of air inlets, comprising: a plurality of first gaseous materials, a second gaseous material and a third gaseous material respectively At least one first air inlet, one second air inlet, and one third air inlet of the supply; (b) at least one exhaust port capable of receiving exhaust gas from the deposition of the film material and at least two extended exhaust gases a channel, each of the extended exhaust passages being in gaseous communication with the at least one exhaust port; (c) at least three sets of extended injection passages, (i) the first set comprising one or more first extended injections a channel, (ii) the second group includes one or more second extended jet channels, and (iii) the third group includes at least two third extended jet channels, the first, second, and third extended jet channels Each of the first, second, and third extended injection channels can be in gaseous communication with one of the respective first, second, and third intake ports; Is substantially parallel to each of the extended exhaust passages Extending in a length direction; wherein each of the first extended injection channels has a relatively close extended exhaust passage and a relatively far third extended jet passage and a nearest adjacent second extended jet on at least one extended side thereof Separating the channels; wherein each of the first extended jet channels and each of the second extended jet channels are located between the relatively closer extended exhaust channels and the relatively far extended jet channels; (d) a gas diffuser, and the At least one of the three sets of extended jet channels are associated such that at least one of the first gaseous material, the second gaseous material, and the third gaseous material are capable of being transported therefrom during deposition of the thin film material on the substrate, respectively Passing the gas diffuser before the device is delivered to the substrate, and wherein the gas diffuser maintains each of the first, second, and third gaseous materials in each of the at least one set of extended jet channels Downstream flow separation; wherein a representative gas is assumed to be nitrogen at 25 ° C and a representative average velocity of one of the gaseous materials passing through the gas diffuser is between 0.01 and 0.5 m/sec The gas diffuser to provide a coefficient of friction of greater than 1 × 10 ² of. The conveying device of claim 1, wherein the gas diffuser is associated with each of the three sets of extended injection passages such that each of the first gaseous material, the second gaseous material, and the third gaseous material Respectively capable of independently transferring from the delivery device to the substrate during deposition of the film material on the substrate, and wherein the gas diffuser maintains each of the first, second, and third gaseous materials in the three sets of extensions Flow separation downstream of each of the extended injection passages in the injection passage. The delivery device of claim 2, wherein the gas diffuser is a mechanical assembly for positioning a separate flow path associated with each of the first extended injection channels, and the second extended injection channel Each of the associated independent flow paths and independent flow paths associated with each of the third extended injection channels. The conveying device of claim 1, wherein the gas diffuser occupies a respective extended injection passage of at least one of the three sets of extended injection passages At least part. The delivery device of claim 1, wherein the gas diffuser element is capable of providing a coefficient of friction between 1 x 10 ⁴ and 1 x 10 ⁸ . The conveying device of claim 1, wherein there are at least two second extended injection passages, and wherein each of the first extended injection passages has a relatively closer extended exhaust passage and a relatively far third on its two extended sides The extended jet channel is separated from the most adjacent second extended jet channel. The conveying device of claim 1, wherein there are a plurality of second extended injection passages and a plurality of first extended injection passages; wherein each of the first extended injection passages has a relatively proximally extending exhaust passage on its two extended sides and a relatively long third extended injection channel is separated from the nearest second extended injection channel; and wherein each of the second extended injection channels has a relatively proximally extending exhaust passage and a relatively far side on its two extended sides The third extended jet channel is separated from the most adjacent first extended jet channel. The delivery device of claim 7, wherein the delivery device includes another first or second extended ejection channel at each of the two ends of the delivery head, the delivery head being on its side, in the closest The side of an edge of the output face of one of the conveyors does not have a second or first extended jet channel. The delivery device of claim 2, wherein the gas diffuser is a unit that is designed to be separable from a delivery assembly that forms the remainder of the delivery device, and that substantially covers the delivery assembly for the first Most downstream of the gaseous material, the second gaseous material, and the third gaseous material Flow path. The delivery device of claim 1, wherein the gas diffuser is designed as an inseparable portion of the delivery device. The delivery device of claim 1 wherein the gas diffuser comprises a mechanically formed assembly comprising interconnecting openings in at least two of the elements thereby providing a desired coefficient of friction. The delivery device of claim 11, wherein the at least two components are steel and the interconnect openings are formed by molding, machining, or laser or lithography techniques. The delivery device of claim 2, wherein for each of the first, second, and third extended injection channels, the gas diffuser comprises at least two vertical stacks respectively in at least two vertically disposed gas diffuser plates Providing a passageway that provides a flow path of a gaseous material in combination, the flow path comprising two substantially vertical flow paths separated by a generally horizontal flow path, wherein the substantially vertical flow path is parallel to the respective extension Provided by a passage or passage assembly extending in the direction of extension of the jet passage, and wherein the substantially horizontal flow path is provided by a relatively narrow space between parallel surface regions in the parallel gas diffuser plate, wherein the vertical finger is relative to the The orthogonal direction of the output face of one of the conveyors. The delivery device of claim 13, wherein the at least two vertically disposed gas diffuser plates have a generally horizontally elongated surface on each side and form a substantially flat stacked orifice plate. The delivery device of claim 13, wherein the gas diffuser comprises at least three sets of verticals respectively in at least three vertically disposed gas diffuser plates The stacked passages are defined by a thickness of a central gas diffuser plate positioned between two substantially parallel gas diffuser plates. The delivery device of claim 1, wherein the gas diffuser is a multi-stage system comprising a series of at least three substantially horizontally elongated gas diffuser plates having one of the output faces relative to one of the delivery devices a substantially parallel surface facing each other in orthogonal directions, each of the gas diffuser plates having a plurality of flow passages, each of each of the first, second, and third extended injection passages Extending the jet passage gas communication; wherein at least two of the gas diffuser plates sequentially extend the plurality of passages in the first and third diffuser plates in an extension direction, and wherein the first gas diffuser plate is Each of the plurality of passages is horizontally offset in a direction perpendicular to the length of the extension direction with respect to each of the plurality of passages in the third diffuser plate in fluid communication with the gas; a second gas diffuser plate sequentially positioned between the first and third diffuser plates includes a plurality of extended center openings, each of each of the first and third diffuser plates The width of the corresponding passage in fluid communication therewith is relatively wide such that each extension center opening is defined by two extension sides and the first diffuser assembly and the third diffuser panel are The horizontally transmissive path of fluid communication is contained within its boundaries; and thus the gas diffuser is capable of substantially deflecting the flow of gaseous material therethrough. The delivery device of claim 11, wherein the gas diffuser unit is capable of deflecting the flow at an angle of 45 to 135 degrees such that the orthogonal flow is changed to a parallel with respect to a surface of one of the output faces of the delivery device flow. The delivery device of claim 11, wherein the gas diffuser sequentially provides (i) a substantially vertical flow of gaseous material through the one or more passages or passage components of the at least two components, and (ii) a gaseous material a substantially horizontal flow in a narrow space formed between substantially parallel surface regions of the at least two elements, wherein the narrow space in the vertical cross section forms an extension channel parallel to one of the associated extended ejection channels, wherein the vertical It is meant that the output face of one of the conveyors is at right angles and the level is parallel with respect to the output face of the conveyor. The delivery device of claim 16, wherein the passages in the first gas diffuser plate comprise a plurality of individual sets of perforations extending along an extension line, wherein the perforations of the respective sets are in the second gas diffuser plate One of the pathways is in gaseous communication. The delivery device of claim 1, wherein each of the at least one of the three sets of extended spray channels is designed to at least one of the first gaseous material, the second gaseous material, and the third gaseous material One indirectly provided to the substrate after passing through a porous material in a position: (i) within each of the at least one set of extended jet channels; and/or (ii) the at least one set of extensions Upstream of the individual jet extension channels in the jet channel. The delivery device of claim 20, wherein the porous material comprises The pores formed or formed in a naturally occurring porous material. The delivery device of claim 21, wherein the porous material comprises pores having an average diameter of less than 10,000 nm, the volume of which is substantially for the flow of gaseous material. The delivery device of claim 20, wherein the porous material comprises pores formed by gaps between the particles or pores of interconnected voids formed by a pore former in a solid material. The delivery device of claim 20, wherein the porous material is formed from microfibers. The delivery device of claim 20, wherein the porous material comprises an isolated non-attached pore structure, wherein the pores are substantially perpendicular to the surface. The delivery device of claim 20, wherein the porous material is an alumina material formed from anodized aluminum. A delivery device according to claim 20, wherein the porous material comprises one or more layers of different porous materials or a layer of porous material supported by a perforated sheet, the layers being separated by spacer elements as appropriate. The delivery device of claim 20, wherein the porous material comprises a layer having a thickness of from 5 to 1000 microns. The delivery device of claim 20, wherein the porous material is formed by a gap between inorganic or organic particles bonded together by bonding. A delivery device according to claim 20, wherein the porous material is obtained by treating a polymer film to produce porosity. The delivery device of claim 20, wherein the porous material is at least one covered Covering the form of the horizontal placement layer of the end face of the conveyor. The delivery device of claim 20, wherein the porous material forms a continuous layer that optionally has a passageway formed therein mechanically. The delivery device of claim 32, wherein the mechanically formed openings are extension channels for venting gaseous material back through the delivery device relatively unimpeded. The delivery device of claim 20, wherein the layer of porous material is in the form of a substantially continuous sheet of one of a plurality of sheets. The delivery device of claim 20, wherein the gas diffuser is a component assembly in which the porous material is held in a separate enclosure. The delivery device of claim 20, wherein the porous material is introduced or formed in the extension channel, wherein the extension channels are at least partially filled with the porous material. The delivery device of claim 36, wherein the extension channels are extension channels in a steel sheet into which particles are introduced and subsequently sintered to form a gas diffuser element or portion thereof. A conveying device for depositing a thin film material on a substrate, comprising: (a) a plurality of air inlets, comprising: a plurality of first gaseous materials, a second gaseous material and a third gaseous material respectively At least one first air inlet, one second air inlet, and one third air inlet of the supply; (b) at least one exhaust port capable of receiving exhaust gas from the deposition of the film material and at least two extended exhaust gases a channel, each of the extended exhaust passages being in gaseous communication with the at least one exhaust port; (c) at least three sets of extended jet channels, (i) the first set comprising one or more first extended jet channels, (ii) the second set comprising one or more second extended jet channels, and (iii) a third The set includes at least two third extended injection passages, each of the first, second, and third extended injection passages being capable of being associated with the respective first intake port, second intake port, and third intake port One in gaseous communication; wherein each of the first, second, and third extended injection passages is elongated in a length direction substantially parallel to each of the extended exhaust passages; The first extended injection passage is separated on at least one of its extended sides by a relatively proximally extending exhaust passage and a relatively farther third extended injection passage and a most adjacent second extended injection passage; wherein each of the first extended injections The passage and each of the second extended injection passages are located between the relatively adjacent extended exhaust passages and between the relatively extended extended injection passages; (d) a gas diffuser and at least one of the three sets of extended injection passages Grouping to make the first gaseous material, At least one of the second gaseous material and the third gaseous material can respectively pass through the gas diffuser during deposition of the thin film material on the substrate from the transport device to the substrate, and wherein the gas diffuser maintains Flow separation of the at least one of the first, second, and third gaseous materials downstream of each of the at least one set of extended jet channels; wherein the gas diffuser comprises a porous material, the first gaseous material And at least one of the second gaseous material and the third gaseous material Pass through the porous material. A conveying device for depositing a thin film material on a substrate, comprising: (a) a plurality of air inlets, comprising: a plurality of first gaseous materials, a second gaseous material and a third gaseous material respectively At least one first air inlet, one second air inlet, and one third air inlet of the supply; (b) at least one exhaust port capable of receiving exhaust gas from the deposition of the film material and at least two extended exhaust gases a channel, each of the extended exhaust passages being in gaseous communication with the at least one exhaust port; (c) at least three sets of extended injection passages, (i) the first set comprising one or more first extended injections a channel, (ii) the second group includes one or more second extended jet channels, and (iii) the third group includes at least two third extended jet channels, the first, second, and third extended jet channels Each of the first, second, and third extended injection channels can be in gaseous communication with one of the respective first, second, and third intake ports; wherein each of the first, second, and third extended injection channels In substantially parallel with each of the extended exhaust passages Extending in a directional direction; wherein each of the first extended injection channels is separated from the most adjacent third extended injection channel by a relatively closer extended exhaust channel and a relatively farther third extended jet channel on at least one extended side thereof; Wherein each of the first extended injection channels and each of the second extended injection channels are located between the relatively adjacent extended exhaust channels and the relatively far extended extended injection channels; (d) a gas diffuser associated with at least one of the three sets of extended jet channels such that at least one of the first gaseous material, the second gaseous material, and the third gaseous material are capable of The film material on the substrate is deposited through the gas diffuser prior to being transported from the transport device to the substrate, and wherein the gas diffuser maintains the at least one of the first, second, and third gaseous materials at least a flow separation downstream of each of the plurality of extended jet channels; wherein the gas diffuser comprises a mechanically formed assembly comprising a series of at least two components, each component comprising a body facing each other a parallel surface region; wherein at least one of the elements includes a plurality of perforations extending in an extension direction, wherein each of the plurality of perforations is associated with a flow from one of the extended ejection channels of the at least one set of extended ejection channels; and wherein The gas diffuser delivers a gaseous material from a plurality of the perforations to a narrow space between the parallel surface regions of the two components Deflection. A deposition system, wherein the delivery device of claim 1 is capable of providing a solid material deposition on a substrate in a system, wherein a film is deposited between an output face of the delivery head and the substrate surface during film deposition Generally uniform distance. The deposition system of claim 40, wherein the pressure generated by the one or more of the gaseous materials flowing from the delivery head to the surface of the substrate for film deposition provides the output face of the delivery head and the At least a portion of the force separating the surface of the substrate. A deposition system according to claim 40, wherein a substrate carrier is a moving web and/or the substrate is a moving web. The deposition system of claim 40, wherein the substrate carrier maintains the substrate surface at a distance of within 0.4 mm from the output face of the delivery head. The deposition system of claim 42, wherein the movement of the web provided by the transport device is continuous, as the case may be reciprocating. The deposition system of claim 40, wherein the substrate and the delivery head are exposed to the atmosphere. The deposition system of claim 40, wherein the gas flow is provided via substantially parallel extending openings on the output face of the delivery head, the openings being substantially straight or substantially concentric. The deposition system of claim 40, wherein the substantially uniform distance between the output face of the delivery head and the substrate is less than 1 mm. A method of depositing a thin film material on a substrate, comprising simultaneously directing a series of gas streams from an output surface of a delivery head toward a surface of a substrate, and wherein the series of gas streams comprises at least a first reactive gaseous material, An inert purge gas and a second reactive gaseous material, wherein the first reactive gaseous material is capable of reacting with a surface of the substrate treated by the second reactive gaseous material; wherein the delivery head comprises a gas diffuser element therethrough Passing at least one of the first reactive gaseous material, the inert purge gas, and the second reactive gaseous material while maintaining flow separation of the at least one gaseous material; wherein during deposition of the thin film material on the substrate, The gas diffuser provides a coefficient of friction greater than 1 x 10 ² for the gaseous material passing therethrough. The method of claim 48, wherein the gas diffuser comprises a mechanically formed assembly comprising a series of at least two elements, each element comprising a substantially parallel surface area facing each other; each element comprising a respective mutual a communication path, each interconnecting passage being in fluid communication with one of the at least one set of extended injection passages; wherein the gas diffuser is provided by two separate separations for a substantially horizontal flow path for one of the gaseous materials a substantially vertical flow path of the gaseous material deflecting the gaseous material therethrough; wherein each substantially vertical flow path is in a direction parallel to the output face of the delivery device and parallel to the extended spray channels Extending one or more interconnecting passages or component passages to provide; and each of the generally horizontal flow paths is provided by a narrow space between the parallel surface regions of the two elements, wherein the vertical fingers are relative to The orthogonal direction of the output face of the conveyor means and horizontally refers to the parallel direction with respect to the output face of the conveyor. The method of claim 48, wherein the flow of the first reactive gaseous material and the second reactive gaseous material is substantially spatially separated by at least the inert purge gas and an exhaust outlet/member. The method of claim 48, wherein one or more of the gas streams provide a pressure that at least causes the surface of the substrate to separate from the end surface of the delivery head. The method of claim 48, wherein the gas flow is provided from a series of substantially parallel open extension output channels positioned in close proximity to the substrate, the delivery The output face of the head is within 1 mm of the surface of the substrate subject to deposition. The method of claim 48, wherein a given area of the substrate is exposed to the gas stream of the first reactive gaseous material for less than 500 milliseconds each time. The method of claim 48, further comprising providing relative motion between the delivery head and the substrate. The method of claim 48, wherein the gas flow rate of at least one of the reactive gaseous materials is at least 1 sccm. The method of claim 48, wherein the temperature of the substrate during deposition is less than 300 °C. The method of claim 48, wherein the first reactive gaseous material is a metal-containing compound and the second reactive gaseous material is a non-metal compound. The method of claim 57, wherein the metal-containing compound is a Group II, III, IV, V or VI element of the periodic table. The method of claim 57, wherein the metal-containing compound is an organometallic compound that is vaporizable at a temperature below 300 °C. The method of claim 57, wherein the metal-containing compound reacts with the second reactive gaseous material to form an oxide or sulfide material selected from the group consisting of antimony pentoxide, aluminum oxide, titanium oxide, Antimony pentoxide, zirconia, cerium oxide, zinc oxide, cerium oxide, cerium oxide, cerium oxide, vanadium oxide, molybdenum oxide, manganese oxide, tin oxide, indium oxide, tungsten oxide, cerium oxide, zinc sulfide, Barium sulfide, calcium sulfide, lead sulfide and mixtures thereof. The method of claim 48, wherein the method is for fabricating a semiconductor or dielectric film for use in a transistor, wherein the film comprises a metal oxide based material, the method comprising Forming at least one layer of a metal oxide-based material on a substrate at a temperature of 300 ° C or lower, wherein the metal oxide-based material is a reaction product of at least two reactive gases, a first reaction The gas comprises an organometallic precursor compound and a second reactive gas comprises a reactive oxygen-containing material. The method of claim 48, wherein the gaseous material exiting the extended openings has substantially equal pressures within no more than 10% of the length along the length of the openings. A method of depositing a thin film material on a substrate, comprising simultaneously directing a series of gas streams from an output surface of a delivery head toward a surface of a substrate, and wherein the series of gas streams comprises at least a first reactive gaseous material, An inert purge gas and a second reactive gaseous material, wherein the first reactive gaseous material is capable of reacting with a surface of the substrate treated by the second reactive gaseous material; wherein the gas diffuser comprises a porous material, the first Passing at least one of a reactive gaseous material, the second reactive gaseous material, and the inert purge gas through the porous material, thereby providing a back pressure and in the first reactive gaseous material, the second reactive gaseous state The flow of the at least one of the material and the inert purge gas exits the delivery device to promote pressure balance. The method of claim 63, wherein the gas diffuser comprises a porous material Feeding the first reactive gaseous material, the second reactive gaseous material, and the inert purge gas through the porous material while maintaining flow separation, thereby providing back pressure and promoting interaction with the first reactive gaseous material, A pressure balance associated with the exiting gas flow of the at least one of the second reactive gaseous material and the inert purge gas.